Personal care compositions

ABSTRACT

Emulsion compositions, suitable for personal care applications such as hair styling, and other applications, are disclosed. The compositions comprise: 
     a) a silicone functional polymer having the formula selected from the group consisting of: 
     (AB) n  ; ABA; BAB; ##STR1## and mixtures thereof; wherein B is a silicone moiety comprising repeating units of: ##STR2## R is independently, C1-C30 alkyl, aryl, alkylaryl, haloalkyl, H, or C1-C6 alkoxy, wherein the weight average molecular weight of each silicone moiety B is independently from about 1500 to about 50,000; 
     A is a polar polymeric moiety which is soluble or dispersible in mixtures of ethanol and water containing less than 60% ethanol by weight; and 
     n is an integer of 1 or greater; 
     wherein the molecular weight of the silicone functional polymer is at least about 2,000. 
     b) an organopolysiloxane emulsion comprising: 
     (i) a polyorganosiloxane dispersed as particles in the emulsion, the polyorganosiloxane having an average particle size of less than about 150 nanometers, and 
     (ii) a surfactant system for dispersing the organopolysiloxane in the emulsion; 
     c) a carrier comprising at least about 0.5%, by weight of the composition, of a first solvent selected from the group consisting of water; water soluble organic solvents; organic solvents which are strongly to moderately strong in hydrogen-bonding parameter; and mixtures thereof; wherein the first solvent is other than C 1  -C 3  monohydric alcohol, C 1  -C 3  ketone and C 1  -C 3  ether; 
     wherein the silicone functional polymer is present in an amount effective to stabilize the emulsion in the personal care composition.

TECHNICAL FIELD

The present invention relates to compositions including siliconeemulsions, especially microemulsions, and corresponding applications ofthe compositions, e.g., in personal care areas such as hair care, skincare, and nail care. The compositions are especially useful, e.g., inhair styling applications. The invention further relates to stablecompositions containing a silicone emulsion, especially microemulsions,and lower monohydric alcohol, and corresponding applications of thecompositions.

BACKGROUND OF THE INVENTION

Silicone emulsions have been used in a variety of applications in theareas of personal care (e.g., hair, skin or nail care), household care,automotive care, and coatings. When used, the stability of the emulsionis generally important in order to provide a highly functional andesthetically pleasing product. However, formulations in these areastends to be complex, requiring a number of ingredients for differentpurposes, with potential for incompatibilities. For example, siliconeemulsions tend to be unstable in compositions containing lower alcohols,resulting in phase separation of the composition. Otherincompatibilities in the system, e.g., polymer--polymer orpolymer-surfactant interactions, can also result in phase separation.

For example, silicone emulsions have been used in hair stylingcompositions, e.g., hairsprays, mousses, gels, lotions and the like.Such compositions provide temporary setting benefits and can usually beremoved by water or by shampooing. The materials used in these types ofhair styling compositions are generally resins, gums, and adhesivepolymers which are capable of imparting style or shape to the hair.

Many of these products also contain lower alcohols in order to obtaingood films of the polymer in a short period of time.

Many people desire a high level of style retention, or hold, from astyling product. Unfortunately, most current hair styling productshaving good hold characteristics suffer from the disadvantages of beingeither too stiff, not smooth or too sticky upon drying. Stiffcompositions tend to be brittle and break down under common stressessuch as wind, brushing, combing. Stiff compositions also tend to feeland look unnatural. Sticky compositions overcome many of the foregoingdisadvantages of stiff compositions, because sticky compositions tend tobe more forgiving, i.e., flexible, under stress and allow for restylingof the hair. However, sticky compositions have the disadvantage ofleaving the hair with a heavy, coated feel and with a limp andunattractive appearance. Also, sticky compositions cause the hair toquickly become soiled from common contaminant sources such as dust,dirt, lint, sebum, etc.

When incorporated into a hair styling composition, silicones tend toprovide a desirably smooth or soft hair feel. Unfortunately, siliconeemulsions tend to be difficult to formulate in hair stylingcompositions, which typically contain lower alcohols. As discussedabove, such compositions tend to phase separate. This phase separationis not only undesirable for visual esthetic reasons, but for performancereasons as well. When the product phase separates, hold and/or hair feelproperties of the product tend to be negatively impacted.

Therefore, a need exists for hair styling compositions providing goodstyle retention without the disadvantages of stiff or stickycompositions. There is a particular need for hair styling compositionscontaining lower alcohols providing good style retention without thedisadvantages of stiff or sticky compositions.

A variety of personal care products for treatment of skin and nails arealso known. Many of these products contain alcohols, generally toprovide a volatility to the product for a desired astringency,application or other reason. These products may also contain a siliconefor imparting a desirable skin feel. Examples of such products includedeodorants, antiperspirants, after-shave lotions, nail polish, nailpolish remover, wet wipes, leather conditioners, and spray lubricants.Such products containing lower alcohols and silicone emulsions also tendto suffer from phase separation, which negatively impacts visualesthetics and/or performance of the product. Therefore, a need existsfor topical compositions for treating the skin or nails, containinglower alcohols and silicone emulsions, which are also stable.

It has been discovered that certain silicone functional polymers can beused to stabilize silicone emulsions, silicone microemulsions or acomposition containing such emulsions in the presence of lower alcohols,e.g., C₁ -C₃ monohydric alcohols, which may be included in thecomposition. Stability is provided even where the composition containsrelatively high levels of lower alcohol. While stability with respect toC₁ -C₃ monohydric alcohols, and especially ethanol, propanol andisopropanol, is of greatest interest because of their widespread use incommercial applications, superior stability is also provided tocompositions containing C₁ -C₃ ketones and ethers. Such stability isuseful in a variety of applications, including applications in the areasof personal care, household care, automotive care and coatings.

It is an object of the invention to provide novel silicone functionalpolymers which are useful for stabilizing silicone emulsions in thepresence of an alcohol.

Another object of the invention is to provide stable compositionscontaining certain silicone functional polymers and a suitable carrier,especially carriers containing lower alcohols. It is yet another objectof the invention to provide such compositions which also contain asilicone emulsion.

It is another object of the invention to provide such polymers andcompositions which are suitable for applications in the personal carearea, including hair care, skin care and nail care applications.

It is another object of the invention to provide such polymers andcompositions which are suitable for hair styling, e.g., hair sprays,mousses, gels, lotions and the like.

It is another object of this invention to provide hair stylingcompositions that provide good style retention without unacceptablestiffness or stickiness. Another object of this invention is to providehair styling compositions that both look and feel natural.

It is another object of this invention to provide methods for stylingand holding hair.

These and other objects will become readily apparent from the detaileddescription which follows.

SUMMARY OF THE INVENTION

The present invention relates to personal care compositions, e.g.,compositions which are suitable for application to the skin, hair ornails. The compositions comprise:

a) a silicone functional polymer having the formula selected from thegroup consisting of:

(AB)_(n) ; ABA; BAB; ##STR3## and mixtures thereof; wherein B is asilicone moiety comprising repeating units of: ##STR4##

R is independently, C1-C30 alkyl, aryl, alkylaryl, haloalkyl, H or C1-C6alkoxy, wherein the weight average molecular weight of each siliconemoiety B is independently from about 1500 to about 50,000; and

A is a polar polymeric moiety which is soluble or dispersible,preferably soluble or microdispersible, in mixtures of ethanol and watercontaining less than 60% ethanol by weight;

n is an integer of 1 or greater;

wherein the molecular weight of the silicone functional polymer is atleast about 2000, preferably from about 2,000 to about 1,000,000;

b) an organopolysiloxane emulsion comprising:

(i) a polyorganosiloxane dispersed as particles in the emulsion, thepolyorganosiloxane having an average particle size of less than about150 nanometers, and

(ii) a surfactant system for dispersing the organopolysiloxane in theemulsion;

c) a carrier comprising at least about 0.5%, by weight of thecomposition, of a first solvent selected from the group consisting ofwater; water soluble organic solvents; organic solvents which arestrongly to moderately strong in hydrogen-bonding parameter; andmixtures thereof; wherein the first solvent is other than C₁ -C₃monohydric alcohol, C₁ -C₃ ketone and C₁ -C₃ ether,

wherein the silicone functional polymer is present in an amounteffective to stabilize the emulsion in the personal care composition.

In a preferred embodiment, the composition further comprises a secondsolvent selected from C₁ -C₃ monohydric alcohols, C₁ -C₃ ketones, C₁ -C₃ethers, and mixtures thereof preferably a C₁ -C₃ monohydric alcohol.Compositions of this type preferably comprise water as the firstsolvent. The composition may comprise a hair styling polymer.

DETAILED DESCRIPTION OF THE INVENTION

The essential components of the present invention are described below.Also included is a nonexclusive description of various optional andpreferred components useful in embodiments of the present invention.

The present invention can comprise, consist of, or consist essentiallyof any of the required or optional ingredients and/or limitationsdescribed herein.

All percentages and ratios are calculated on a weight basis unlessotherwise indicated. All percentages are calculated based upon the totalcomposition unless otherwise indicated.

All molecular weights are weight average molecular weights and are givenin units of grams per mole.

All ingredient levels are in reference to the active level of thatingredient, and are exclusive of solvents, by-products, or otherimpurities that may be present in commercially available sources, unlessotherwise indicated.

All measurements made are at ambient room temperature, which isapproximately 73° F., unless otherwise designated.

All documents referred to herein, including all patents, patentapplications, and printed publications, are hereby incorporated byreference in their entirety in this disclosure.

Preferred components and compositions herein are those suitable forapplication to human hair, skin, or nails. The term "suitable forapplication to human hair, skin or nails" or the like, as used herein,means that the compositions or components thereof so described aresuitable for use in contact with human hair, skin (including the scalp)or nails, respectively, without undue toxicity, incompatibility,instability, allergic response, and the like.

The components of the compositions hereof are selected such that thetotal composition will be compatible. As used herein, compatible meansthere is no marked phase separation, e.g., excessive cloudiness,layering or precipitation of the composition which negatively impactsthe esthetic or functional properties of the composition in asignificant manner.

Preferred compositions are those wherein the mixture of essentialcomponents, namely the silicone functional polymer, silicone emulsion,and carrier is a substantially homogeneous solution or dispersion(preferably a micro-dispersion), more preferably substantially clear totranslucent in appearance. Preferred final personal care compositionsare those also characterized by these properties.

Preferred compositions are those wherein the mixture of essentialcomponents provides a % transmittance of at least about 50% at awavelength of 460 nm as determined by standard spectroscopy methods.Preferred final personal care compositions are those also characterizedby these properties.

Silicone Functional Polymers

The compositions of the present invention comprise a silicone functionalpolymer for providing stability to the silicone microemulsion in thecomposition. One or more silicone functional polymers may be used. Thesilicone functional polymer is used in an amount effective to stabilizethe silicone microemulsion in the personal care composition (such thatthe composition will be compatible). The silicone functional polymerassists to prevent or minimize coagulation, agglomeration or coalescenceof teh emulsion particles and their subsequent settling or rising to thesurface. Some settling or rising is acceptable, although not preferred,provided that the particles are readily redispersed by light agitationsuch as shaking. Generally from about 0.01% to about 20%, preferablyfrom about 0.1% to about 15%, more preferably from about 0.5% to about10% of the silicone functional polymer is used.

A variety of silicone functional polymers are suitable in the presentinvention. Particular polymers will be selected by the skilled artisanconsidering the solubility of the polymer in the composition and theionicity of the composition.

Suitable silicone functional polymers are those which are soluble ordispersible (preferably microdispersible) in the carrier describedherein in the weight ratios employed in the composition. Solubility ordispersibilty is determined at ambient conditions of temperature andpressure (25° C., 101.3 kPa (1 Atm)), and after neutralization of thepolymer, if any.

Exemplary silicone functional polymers include the following:

(AB)_(n), ABA, BAB, ##STR5##

Wherein B is a silicone moiety comprising repeating units of: ##STR6##

R can be independently, C1-C30 alkyl, aryl (e.g., phenyl), alkylaryl(e.g., styryl), haloalkyl, H, and C1-C6 alkoxy, wherein the molecularweight of the silicone moiety is about 1500 to about 50,000, morepreferably about 2,000 to about 40,000, and most preferably about 2,000to about 30,000;

A is a polar polymeric moiety of any monomer composition provided thatthe silicone functional polymer is soluble or dispersible (preferablymicro-dispersible) at 25° C., 101.3 kPa (1 Atm) in mixtures of ethanoland water where the ethanol content is less than 60% by weight.Solubility/dispersibility in such mixtures is present where theresulting mixture is substantially clear to translucent in appearanceand the mixture is compatible. Suitable A moieties include acrylic andvinyl polymers, polyalkyloxazolines, proteins, sugars andpolysaccharides. Exemplary acrylics and vinyls are as described below inreference to silicone graft polymers; and

n is an integer of 1 or more, preferably 1.

The molecular weight of the silicone functional polymer is at leastabout 2000, preferably from about 2,000 to about 1,000,000, morepreferably from about 2,000 to about 150,000, still more preferably fromabout 3,000 to about 50,000, and most preferably from about 3,000 toabout 20,000.

Suitable silicone functional polymers include graft and block copolymerscomprising silicone with a nonsilicone, polar polymer. Whether graft orblock, these copolymers should satisfy the following four criteria:

(1) the silicone portion is covalently attached to the non-siliconeportion;

(2) the molecular weight of the silicone portion is greater than 1500,preferably at least about 2,000, and up to about 50,000; and

(3) the non-silicone portion must render the entire copolymer soluble ordispersible in the personal care composition vehicle.

Suitable silicone functional copolymers include the following:

(i) Silicone Graft Copolymers

Silicone graft copolymers suitable for the present invention areexemplified by the formulas ##STR7## where the first structure has thesilicone grafted to the non-silicone backbone, and the second has thenon-silicone portion grafted to the silicone backbone, and x, y, p and sare as defined above.

Such graft copolymers can be prepared by a number of methods known tothose skilled in the art, including:

1. Incorporation of silicone macromonomers in free radicalpolymerization. Such silicone functional polymers include the siliconegraft copolymers described, along with methods of maling them, in U.S.Pat. No. 5,658,557, Bolich et al., issued Aug. 19, 1997, U.S. Pat. No.4,693,935, Mazurek, issued Sep. 15, 1987, and U.S. Pat. No. 4,728,571,Clemens et al., issued Mar. 1, 1988, each incorporated herein byreference.

2. Incorporation of silicone macromonomer in atom transfer radicalpolymerization. A method of making these types of polymers is generallydescribed in Beers et al, "The Use of `Living` Radical Polymerization toSynthesize Graft Copolymers," Polymer Preprints, pp 571-572, March,1996, incorporated herein by reference.

3. Incorporation of vinyl polymeric grafts onto a silicone backbone bychain transfer to a pendant sulfhydryl group. Such sulfur linkedsilicone copolymers are described in detail in U.S. Pat. No. 5,468,477,to Kumar et al., issued Nov. 21, 1995, and PCT Application No. WO95/03776, assigned to 3M, published Feb. 9, 1995, which are incorporatedby reference herein in their entirety. Additional patents with sulfurlinked structures include U.S. Pat. No. 5,032,460, to Kanter et al,issued Jul. 16, 1991, assigned to 3M and U.S. Pat. No. 5,362,485, toHayama et al, issued Nov. 8, 1994, assigned to Mitsubishi Chem. Co.

Preferred silicone functional polymers are the silicone graft copolymersdescribed, along with methods of making them, in the above referencedand incorporated U.S. Pat. No. 5,658,557, Bolich et al., issued Aug. 19,1997, U.S. Pat. No. 4,693,935, Mazurek, issued Sep. 15, 1987, and U.S.Pat. No. 4,728,571, Clemens et al., issued Mar. 1, 1988. In addition tostabilizing the silicone microemulsion, these silicone-containingcopolymers provide hair conditioning and/or hair setting characteristicsto the composition.

These polymers include copolymers having a molecular weight of fromabout 2,000 to about 1,000,000, which have a vinyl polymeric backbonecomprising acrylate groups and having grafted to it monovalent siloxanepolymeric moieties, the copolymer comprising C monomers and componentsselected from the group consisting of A monomers, B monomers, andmixtures thereof. A is at least one free radically polymerizable vinylmonomer, and the amount by weight of A monomer, when used, is up toabout 90% of the total weight of all monomers in the copolymer. B is atleast one reinforcing monomer copolymerizable with A, and the amount byweight of B monomer, when used, is up to about 98% of the total weightof all monomers in the copolymer. The B monomer is selected from thegroup consisting of polar monomers and macromers. At least one of the Aor B monomers comprise an acrylate monomer. C comprises from about 0.01%to about 80% of the copolymer and is a polymeric monomer having amolecular weight of at least 1,500, preferably at least about 2,000, upto about 50,000 and the general formula

    X(Y).sub.n Si(R).sub.3-m (Z).sub.m

wherein

X is a vinyl group copolymerizable with the A and B monomers

Y is a divalent linking group

R is a hydrogen, lower alkyl (preferably C₁ -C₅, more preferably C₁-C₃), aryl or alkoxy

Z is a monovalent siloxane polymeric moiety having a number averagemolecular weight of at least about 1500, is essentially unreactive undercopolymerization conditions, and is pendant from the vinyl polymericbackbone after copolymerization

n is 0 or 1, and

m is an integer from 1 to 3.

In another embodiment, the silicone-acrylate copolymer has a vinylpolymeric backbone comprising acrylate groups and grafted to thebackbone a polydimethylsiloxane macromer having a weight averagemolecular weight of at least 1,500, preferably at least about 2,000, andup to about 50,000, preferably from about 2,000 to about 40,000, mostpreferably about 3000 to about 30,000.

The polymers should have a weight average molecular weight of from about2,000 to about 1,000,000 (preferably from about 2,000 to about 150,000).

As used herein, "acrylate monomer" means acrylic acid and derivativesthereof e.g., esters of acrylic acid. The acid of derivatives may besubstituted, e.g., with alkyl groups.

Representative examples of A (hydrophobic) monomers are acrylic ormethacrylic acid esters of C₁ -C₁₈ alcohols, such as methanol, ethanol,methoxy ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol,1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol,1-methyl-1-butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol,2-methyl-1-pentanol, 3-methyl-1-pentanol, t-butanol(2-methyl-2-propanol), cyclohexanol, neodecanol, 2-ethyl-1-butanol,3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-1-heptanol,2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol,1-decanol, 1-dodecanol, 1-hexadecanol, 1-octadecanol, and the like, thealcohols having from about 1-18 carbon atoms with the average number ofcarbon atoms being from about 4-12; styrene; vinyl acetate; vinylchloride; vinylidene chloride; vinyl propionate; alpha-methylstyrene;t-butylstyrene; butadiene; cyclohexadiene; ethylene; propylene; vinyltoluene; and mixtures thereof. Preferred A monomers are the acrylic ormethacrylic acid esters of C₁ -C₁₈ alcohols, more preferably n-butylmethacrylate, isobutyl methacrylate, t-butyl acrylate, t-butylmethacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, andmixtures thereof.

Representative examples of B monomers (hydrophilic) include acrylicacid, methacrylic acid, N,N-dimethylacrylamide, dimethylaminoethylmethacrylate, quaternized dimethylaminoethyl methacrylate,methacrylamide, N-t-butyl acrylamide, maleic acid, maleic anhydride andits half esters, crotonic acid, itaconic acid, acrylamide, acrylatealcohols, hydroxyethyl methacrylate, diallyldimethyl ammonium chloride,vinyl pyrrolidone, vinyl ethers (such as methyl vinyl ether),maleimides, vinyl pyridine, vinyl imidazole, other polar vinylheterocyclics, styrene sulfonate, allyl alcohol, vinyl alcohol (producedby the hydrolysis of vinyl acetate after polymerization) vinylcaprolactam, and mixtures thereof. Preferred B monomers include acrylicacid and derivatives thereof, vinyl pyrrolidone, and mixtures thereof.More preferred B monomers are N,N-dimethylacrylamide, dinethylaminoethylmethacrylate, quaternized dimethylaminoethyl methacrylate, vinylpyrrolidone, and mixtures thereof.

Preferably, the C monomer has a formula selected from the followinggroup: ##STR8##

In those structures, m is 1, 2 or 3 (preferably m=1); p is 0 or 1,preferably 0; R" is alkyl or hydrogen; q (in all but (III) is an integerfrom 2 to 6; and q in (III) is an integer from 0 to 6; X is ##STR9##

R¹ is hydrogen or --COOH; R² is hydrogen, methyl or --CH₂ COOH; Z is##STR10## R4 is alkyl, alkoxy, alkylamino, aryl, or hydroxyl (preferablyR4 is alkyl); and r is an integer from about 5 to about 700.

The silicone graft polymers generally comprise from 0% to about 90%(preferably from about 5% to about 90%, more preferably from about 20%to about 90%) of monomer A, from about 0% to about 98% (preferably fromabout 7.5% to about 80%) of monomer B, and from about 1% to about 70%(preferably from about 1% to about 60%, most preferably from about 2% toabout 50%) of monomer C. The combination of the A and B monomerspreferably comprises from about 30.0% to about 99% (more preferablyabout 40% to about 98%, most preferably from about 40% to about 95%) ofthe polymer. The composition of any particular copolymer will helpdetermine its formulational properties. In fact, by appropriateselection and combination of particular A, B and C components, thecopolymer can be optimized for inclusion in specific vehicles. Forexample, polymers which are soluble or dispersible in an aqueousformulation preferably have the composition: from about 0% to about 70%(preferably from about 5% to about 70%) monomer A, from about 10% toabout 98% (preferably from about 10% to about 80%, more preferably fromabout 10% to about 60%) monomer B, and from about 1% to about 50%monomer C.

Particularly preferred polymers for use in the present invention includethe following (the weight percents below refer to the amount ofreactants added in the polymerization reaction, not necessarily theamount in the finished polymer):

(A) acrylic acid/n-butylmethacrylate/(polydimethylsiloxane (PDMS)macromer--3,000 molecular weight) (50/10/40 w/w/w), M.W.=20,000

(B) N,N-dimethylacrylamide/isobutyl methacrylate/(PDMS macromer--2,000molecular weight) (35/5/60 w/w/w), M.W.=10,000

(C) N,N-dimethylacrylamide/(PDMS macromer--4,000 molecular wt) (80/20w/w), M.W.=20,000

(D) t-butylacrylate/acrylic acid/(PDMS macromer--3,000molecular wt)(40/40/20 w/w/w), M.W.=12,000

(E) t-butylacrylate/acrylic acid/(PDMS macromer - 12,000-14,000molecular wt) (65/25/10 w/w/w), M.W.=80,000

(ii) Silicone Block Copolymers

Silicone block copolymers suitable for the present invention areexemplified by the formula

    (AB).sub.n, ABA, BAB

where n is an integer 1 or greater, that is, the block copolymers can bediblocks, multiblocks, or triblocks. These graft copolymers can be madeby a number of methods known to those skilled in the art, including:

1. Formation of silicone/vinyl polymeric block copolymers using siliconemacroinitiators. The polymers can be prepared according to the methoddescribed in Macromolecular Design, Concepts and Practice, M. K. Mishra,Ed, Polymer Frontiers International, Inc, 1994, Chapter 8.

2. Incorporation of silicone blocks using atom transfer radicalpolymerization. The polymers may be prepared according to the methoddescribed in "Development of Novel Attachable Initiator for LivingRadical Polymerization and Synthesis of Polysiloxane Block Copolymer;"Yoshiki Nakagawa and Krzysztof Matyjaszewski; pages 270-271; PolymerPreprints, August 1996.

3. Cationic polymerization onto the ends of a silicone terminated with acationic polymerization initiator. Such block copolymers are describedin more detail in U.S. Pat. No. 4,659,777, to Riffle et al., issued Apr.21, 1987, incorporated herein by reference.

Useful herein are silicone block copolymers comprising repeating blockunits of polysiloxanes.

Examples of silicone-containing block copolymers are found in U.S. Pat.No. 5,523,365, to Geck et al., issued Jun. 4, 1996; U.S. Pat. No.4,689,289, to Crivello, issued Aug. 25, 1987; U.S. Pat. No. 4,584,356,to Crivello, issued Apr. 22, 1986; Macromolecular Design, Concept &Practice, Ed: M. K. Mishra, Polymer Frontiers International, Inc.,Hopewell Jct., N.Y. (1994), and Block Copolymers, A. Noshay and J. E.McGrath, Academic Press, NY (1977), which are all incorporated byreference herein in their entirety. Other silicone block copolymerssuitable for use herein are those described, along with methods ofmaking them, in the above referenced and incorporated U.S. Pat. No.5,658,577.

Silicone-containing block copolymers useful in the present inventioninclude those which can be described by the formulas A--B, A--B--A,--(A--B)_(n) -- and B--A--B wherein n is an integer of 2 or greater.A--B represents a diblock structure, A--B--A represents a triblockstructure, and --(A--B)_(n) -- represents a multiblock structure. Theblock copolymers can comprise mixtures of diblocks, triblocks, andhigher multiblock combinations as well as small amounts of homopolymers.

The silicone block portion, B, can be represented by the followingpolymeric structure

    --(SiR.sub.2 O).sub.m --,

wherein each R is independently selected from the group consisting ofhydrogen, hydroxyl, C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₂ -C₆ alkylamino,styryl, phenyl, C₁ -C₆ alkyl or alkoxy-substituted phenyl, preferablywherein R is methyl. In the preceding formula, m is an integer of about10 or greater, m is an integer of about 40 or greater, more preferablyof about 60 or greater, and most preferably of about 100 or greater.

The nonsilicone block, A, when formed by a synthetic process usingradical polymerization, comprises monomers selected from the monomers asdescribed above in reference to the A and B monomers for the siliconegrafted copolymers. The block copolymers preferably contain up to about80% (preferably from about 10% to about 70%) by weight of one or morepolydimethyl siloxane blocks and one or more non-silicone blocks(preferably acrylates or vinyls).

Other silicone block copolymers useful are exemplified in U.S. Pat. No.4,659,777, to Riffle and Yilgor, issued Apr. 21, 1987, assigned toThoratec Laboratories. The non-silicone part of these blocks arepoly(oxazoline). A preferred silicone block is an ABA where each A blockis 3,000 M.W. poly(ethyl oxazoline) and the polydimethyl siloxane blockM.W. is 3,000.

Additional silicone block copolymers suitable for use herein includethose described in U.S. patent application Ser. No. 08/939,362, filedSep. 29, 1997 in the names of Midha, Bolich and Jividen, AttorneysDocket No. 6591R, which is incorporated herein by reference in itsentirety.

(iii) Sulfur-Linked Silicone Containing Copolymers

Also useful herein are sulfur-linked silicone containing copolymers,including block copolymers. As used herein in reference to siliconecontaining copolymers, the term "sulfur-linked" means that the copolymercontains a sulfur linkage (i.e., --S--), a disulfide linkage (i.e.,--S--S--), or a sulfhydryl group (i.e., --SH).

These sulfur-linked silicone containing copolymers are represented bythe following general formula: ##STR11## wherein

G₅ independently represents monovalent moieties which can independentlybe the same or different selected from the group consisting of alkyl,aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and --ZSA; Arepresents a vinyl polymeric segment consisting essentially ofpolymerized free radically polymerizable monomer, and Z is a divalentlinking group. Useful divalent linking groups Z include but are notlimited to the following: C₁ to C₁₀ alkylene, alkarylene, arylene, andalkoxyalkylene. Preferably, Z is selected from the group consisting ofmethylene and propylene for reasons of commercial availability.

G₆ represents monovalent moieties which can independently by the same ordifferent selected from the group consisting of alkyl, aryl, alkaryl,alkoxy, alkylamino, fluoroalkyl, hydrogen, and --ZSA.

G₂ comprises A.

G₄ comprises A.

R₁ represents monovalent moieties which can independently be the same ordifferent and are selected from the group consisting of alkyl, aryl,alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and hydroxyl.Preferably, R₁ represents monovalent moieties which can independently bethe same or different selected from the group consisting of C₁₋₄ alkyland hydroxyl for reasons of commercial availability. Most preferably, R₁is methyl.

R₂ can independently be the same or different and represents divalentlinking groups. Suitable divalent lining groups include but are notlimited to the following: C₁ to C₁₀ alkylene, arylene, alkarylene, andalkoxyalkylene. Preferably, R₂ is selected from the group consisting ofC₁₋₃ alkylene and C₇ -C₁₀ alkarylene due to ease of synthesis of thecompound. Most preferably, R₂ is selected from the group consisting of--CH₂ --, 1,3-propylene, and ##STR12##

R₃ represents monovalent moieties which can independently be the same ordifferent and are selected from the group consisting of alkyl, aryl,alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and hydroxyl.Preferably, R₃ represents monovalent moieties which can independently bethe same or different selected from the group consisting of C₁₋₄ alkyland hydroxyl for reasons of commercial availability. Most preferably, R₃is methyl.

R₄ can independently be the same or different and represents divalentlining groups. Suitable divalent linking groups include but are notlimited to the following: C₁ to C₁₀ alkylene, arylene, alkarylene, andalkoxyalkylene. Preferably, R₄ is selected from the group consisting ofC₁₋₃ alkylene and C₇ -C₁₀ alkarylene for ease of synthesis. Mostpreferably, R₄ is selected from the group consisting of --CH₂ --,1,3-propylene, and ##STR13##

x is an integer of 0-3;

y is an integer of 20 or greater; preferably y is an integer rangingfrom about 20 to about 700, preferably from about 20 to about 200;

q is an integer of 0-3;

wherein at least one of the following is true:

q is an integer of at least 1;

x is an integer of at least 1;

G₅ comprises at least one --ZSA moiety;

G₆ comprises at least one --ZSA moiety.

As noted above, A is a vinyl polymeric segment formed from polymerizedfree radically polymerizable monomers. The selection of A is typicallybased upon the intended uses of the composition, and the properties thecopolymer must possess in order to accomplish its intended purpose. If Acomprises a block in the case of block copolymers, a polymer having ABand ABA architecture will be obtained depending upon whether a mercaptofunctional group --SH is attached to one or both terminal silicon atomsof the mercapto functional silicone compounds, respectively. The weightratio of vinyl polymer block or segment, to silicone segment of thecopolymer can vary. The preferred copolymers are those wherein theweight ratio of vinyl polymer segment to silicone segment ranges fromabout 98:2 to 50:50, in order that the copolymer possesses propertiesinherent to each of the different polymeric segments while retaining theoverall polymer's solubility.

Sulfur linked silicone copolymers are described in more detail in U.S.Pat. No. 5,468,477, to Kumar et al., issued Nov. 21, 1995, and PCTApplication No. WO 95/03776, assigned to 3M, published Feb. 9, 1995,which are incorporated by reference herein in their entirety. Additionalpatents with sulfur linked structures include U.S. Pat. No. 5,032,460,to Kanter et al, issued Jul. 16, 1991, assigned to 3M and U.S. Pat. No.5,362,485, to Hayama et al, issued Nov. 8,1994, assigned to MitsubishiChem. Co.

Organopolysiloxane Emulsions

Preferred compositions of the present invention also contain anorganopolysiloxane emulsion comprising polysiloxane particles dispersedin a suitable carrier, generally with the aid of a surfactant. Theorganopolysiloxane emulsion is generally an aqueous emulsion ormicroemulsion of an organopolysiloxane stabilized in the emulsion ormicroemulsion by one or more ionic or nonionic surfactants. Suchemulsions and microemulsions can be prepared mechanically or by emulsionpolymerization. Emulsions and microemulsions used in the presentinvention are preferably those prepared by emulsion polymerization.

The emulsion is preferably included in an amount such that thecomposition contains from about 0.01 to about 10% of the dispersedpolysiloxane, more preferably about 0.05% to about 6%, most preferablyabout 0.1% to about 4%. Typically, the composition will include about0.02 to about 50% of the emulsion.

Organopolysiloxane emulsions can be classified according to the averageparticle size, or diameter, of the dispersed organopolysiloxane in theemulsion. Emulsions prepared by emulsion polymerization generallycomprise an organopolysiloxane as dispersed particles having a diameterof less than about 140 nanometers, more generally less than about 50nanometers (often referred to as "microemulsions"). Fine emulsions aregenerally those containing particles of organopolysiloxane with adiameter of about 140-300 nanometers, while standard emulsions aregenerally those containing organosiloxane particles with a diametergreater than about 300 nanometers. Particle size of an emulsion can bedetermined by conventional methods, e.g., using a Leeds & NorthrupMicrotrac UPA particle sizer. Microemulsions are preferred for useherein.

The average particle size of the emulsion used in the present inventionis preferably less than about 150 nanometers, more preferably less thanabout 100 nanometers, even more preferably less than about 80nanometers, still more preferably less than about 60 nanometers, mostpreferably less than about 40 nanometers. Silicone emulsions havingthese particle sizes tend to be more stable and have better externalappearance than those having larger particle sizes.

The organopolysiloxane in the emulsion can be a linear or branched chainsiloxane fluid having a viscosity of about 20-3,000,000 mm² /s (cs),preferably 300-300,000 cs, more preferably 350-200,000 cs, at 25° C.

Suitable organopolysiloxanes preferably contain the difunctionalrepeating "D" unit: ##STR14## wherein n is greater than 1 and R¹ and R²are each independently C₁ -C₇ alkyl or phenyl. A mixture of siloxanesmay be used. Exemplary siloxanes include polydimethylsiloxane,polydiethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane,and polydiphenylsiloxane. Siloxane polymers with dimethylsiloxane "D"units are preferred from an economic standpoint. However, R¹ and R² mayindependently be a functional group other than methyl, e.g., aminoalkyl,carboxyalkyl, haloalkyl, acrylate, acryloxy, acrylamide, mercaptoalkylor vinyl.

The siloxane may be terminated with hydroxy groups, alkoxy groups suchas methoxy, ethoxy, and propoxy, or trimethylsiloxy groups, preferablyhydroxy or trimethylsiloxy.

The organopolysiloxane emulsions used herein can be produced by theemulsion polymerization of organosiloxane having a low degree ofpolymerization in a solvent comprising water. The organopolysiloxane isstabilized in the emulsion by a surfactant, e.g., a nonionic surfactantand an ionic surfactant. The degree of polymerization (DP) of thepolysiloxane after emulsion polymerization is preferably in the range offrom 3 to 5,000, more preferably in the range of from 10 to 3,000.

The emulsion can be prepared by the emulsion polymerization processdescribed in EP 459500 (published Dec. 4, 1992), incorporated herein byreference. In that process, stable, oil free polysiloxane emulsions andmicroemulsions are prepared by mixing a cyclic siloxane, a nonionicsurfactant, an ionic surfactant, water, and a condensationpolymerization catalyst. The mixture is heated and agitated atpolymerization reaction temperature until essentially all of the cyclicsiloxane is reacted, and a stable, oil free emulsion or microemulsion isformed. The reaction mix, especially surfactant levels, and conditionsare controlled in order to provide the desired organopolysiloxaneparticle size. The emulsions and microemulsions typically have a pH ofabout 3 to about 10 (e.g., 6-7.5), and contain about 10 to about 70% byweight siloxane polymer, preferably about 20 to about 60%, about 0% toabout 30% by weight nonionic surfactant, about 0 to about 30% by weightionic surfactant, preferably about 0 to about 20%, the balance beingwater. Preferred emulsions and methods of making them are furtherdescribed in U.S. patent application Ser. No. 08/929,721, filed on Sep.15, 1997 in the names of Ronald P. Gee and Judith M. Vincent,incorporated herein by reference in its entirety.

Emulsions can also be produced by the emulsion polymerization processdescribed in EPA 0268982, published Jun. 6, 1988, assigned to Toray,incorporated herein by reference in its entirety. In this process, theemulsion is prepared by a process in which a crude emulsion, consistingof polysiloxane having a low degree of polymerization, a firstsurfactant (anionic, cationic, and nonionic surfactants), and water, isslowly dripped into an aqueous solution containing a catalytic quantityof a polymerization catalyst and a second surfactant which acts as anemulsifying agent (which may be the same as the first surfactant,however, the surfactants should be compatible in the reaction mixtureconsidering the ionicity of the reaction mixture). The reaction mix andconditions are controlled to provide the desired organopolysiloxaneparticle size. Therefore, a dropwise addition of the crude emulsion intothe aqueous solution of catalyst and surfactant of 30 minutes or longeris preferred in order to produce emulsions having smaller particlesizes. In addition, the quantity of surfactant used in the catalyst plusthe surfactant aqueous solution is from about 5 to about 70 weight %,more preferably from about 25 to about 60 per 100 weight partspolysiloxane in the crude emulsion.

Any conventional nonionic surfactant can be used to prepare theemulsion. Exemplary types of nonionic surfactants include siliconepolyethers, both grafted and linear block, ethoxylated fatty alcohols,ethoxylated alcohols, ethoxylated alkyl phenols, Isolaureth-6(polyethylene glycol ether of branched chain aliphatic C₁₂ containingalcohols having the formula C₁₂ H₂₅ (OCH₂ CH₂)₆ OH), fatty acidalkanolamides, amine oxides, sorbitan derivatives (e.g., commerciallyavailable from ICI Americas, Inc., Wilmington, Del., under thetradenames SPAN and TWEEN), and propylene oxide-ethylene oxide blockpolymers (e.g., commercially available from BASF Corp., Parsippany, N.J.under the trademark PLURONIC). Ionic surfactants useful in preparing theemulsion include any conventional anionic surfactant such as sulfonicacids and their salt derivatives. Ionic surfactants also include anyconventional cationic surfactant used in emulsion polymerization.Surfactants of these types are well known in the art and arecommercially available from a number of sources. Specific examples ofthese surfactant types are also disclosed in the above referenced patentapplication Ser. No. 08/929,721.

The surfactant can be used in the form of a single type of surfactant(e.g., anionic, cationic or nonionic), or the surfactant can be used asa combination of two or more types provided that they are compatiblewith each other and the other components of the composition. Preferredcombinations of surfactant types include the combination of two or moretypes of anionic surfactants, the combination of two or more types ofnonionic surfactants, the combination of two or more types of cationicsurfactants, the combination of two or more types of surfactantsselected from both the anionic and nonionic surfactants; and thecombination of two or more types of surfactants selected from both thecationic and nonionic surfactants.

The catalyst employed in the emulsion polymerization may be any catalystcapable of polymerizing cyclic siloxanes in the presence of water,including condensation polymerization catalysts capable of cleavingsiloxane bonds. Exemplary catalysts include strong acids and strongbases, ionic surfactants such as dodecylbenzenesulfonic acid, phasetransfer catalysts, and ion exchange resins where a catalyst is formedin situ. As will be understood by those skilled in the art, a givensurfactant may also serve as the polymerization catalyst (e.g.,alkylbenzenesulfonic acids, or quaternary ammonium hydroxides or saltthereof may function as both a surfactant and the polymerizationcatalyst).

A surfactant system, catalyst and resulting emulsion suitable for use inthe compositions of the present invention can be selected by the skilledartisan considering the ionicity of the composition. In general, thesematerials are selected such that the total composition will becompatible.

Emulsions usefuil herein also include those produced by a mechanicalemulsion process, although those produced by emulsion polymerization arepreferred. In mechanical emulsions, the organopolysiloxane is generallypresent in the emulsion in the form of particles having a diametergreater than about 140 nanometer and less than about 350 nanometer,preferably less than about 300 nanometer. Mechanical emulsions can beprepared by known mechanical processes such as are described in U.S.Pat. No. 5,017,221 (May 21, 1991) and in EP 463431 (Jan. 2, 1992).Typical mechanical emulsions contain a trimethylsiloxy-terminatedpolydimethylsiloxane stabilized by a nonionic surfactant. According tosuch mechanical processes, water, one or more nonionic surfactants, andthe organopolysiloxane are mixed together, and homogenized using alaboratory homogenizer or other device for applying vigorous agitation.These mechanical emulsions typically have a pH of 7-9.5, and contain10-80% by weight of the siloxane, preferably 20-60%, 0.01-15% by weightof the nonionic surfactant(s), the balance being water.

Organopolysiloxane emulsions are available from a number of commercialsources. The following organopolysiloxane emulsions are manufactured byDow Corning of Midland, Mich.

Emulsions containing dimethicone copolyol:

    __________________________________________________________________________                       Internal                                                   Emulsion           phase           Si particle                                Trade Name                                                                            Si Type    viscosity (cps)                                                                      Surfactant                                                                             size, nm                                   __________________________________________________________________________    DC 2-5791 - LP                                                                        Dimethylsiloxanol,                                                                       70-90M Triethanolamine                                                                        123                                                Dimethyl cyclosiloxane                                                                          dodecylbenzene                                                                sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                        DC 2-5791 - MP                                                                        Dimethylsiloxanol,                                                                       70-90M Triethanolamine                                                                         93                                                Dimethyl cyclosiloxane                                                                          dodecylbenzene                                                                sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                        DC 2-5791                                                                             Dimethylsiloxanol,                                                                       70-90M Triethanolamine                                                                        <50                                                Dimethyl cyclosiloxane                                                                          dodecylbenzene                                                                sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                        DC 2-5791 - sp                                                                        Dimethylsiloxanol,                                                                       70-90M Triethanolamine                                                                        <40                                                Dimethyl cyclosiloxane                                                                          dodecylbenzene                                                                sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                        DC 2-5932                                                                             Dimethylsiloxanol,                                                                        1-2M  Cetrimonium                                                                            <30                                                Dimethyl cyclosiloxane                                                                          Chloride, Trideceth-                                                          12                                                  __________________________________________________________________________

    __________________________________________________________________________                       Internal                                                   Emulsion           phase           Si particle                                Trade Name                                                                            Si Type    viscosity (cps)                                                                      Surfactant                                                                             size, nm                                   __________________________________________________________________________    DC 2-1470 - LP                                                                        Dimethylsiloxanol,                                                                       15-20M Triethanolamine                                                                        124                                                Dimethyl cyclosiloxane                                                                          dodecylbenzene                                                                sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                        DC 2-1470 - MP                                                                        Dimethylsiloxanol,                                                                        4-8M  Triethanolamine                                                                         94                                                Dimethyl cyclosiloxane                                                                          dodecylbenzenc                                                                sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                        DC 2 - 1716                                                                           Dimethylsiloxanol with                                                                   10-30M Cetrimonium                                                                            50-80                                      MEM     methyl silsequioxane,                                                                           Chloride, Trideceth-                                        Octamethyl        12                                                          cyclotretrasiloxane                                                   DC 2-8937                                                                             Mercapto-         Cetrimonium                                                                            50-70                                              siloxane          Chloride, Trideceth-                                                          12                                                  DC 2-1470                                                                             Dimethylsiloxanol,                                                                       15-20M Triethanolamine                                                                        <50                                                Dimethyl cyclosiloxane                                                                          dodecylbenzene                                                                sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                        DC 2-1845                                                                             Dimethylsiloxanol,                                                                        4-8M  Triethanolamine                                                                        <40                                                Dimethyl cyclosiloxane                                                                          dodecylbenzene                                                                sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                        DC 2-1845 -                                                                           Dimethylsiloxanol,                                                                       60-70M Triethanolamine                                                                        <35                                        HV      Dimethyl cyclosiloxane                                                                          dodecylbenzene                                                                sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                        DC 2-1550                                                                             Dimethylsiloxanol,                                                                       100-600M                                                                             Triethanolamine                                                                        ≦50                                         Dimethyl cyclosiloxane                                                                          dodecylbenzene                                                                sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                        DC 2-1281                                                                             Dimethylsiloxanol,                                                                        1-2M  Cetrimonium                                                                            <30                                                Dimethyl cyclosiloxane                                                                          Chloride, Trideceth-                                                          12                                                  DC 2-8194                                                                             Dimethyl, aminomethyl                                                                     4-6M  Cetrimonium                                                                            ≦30                                         propyl siloxane   Chloride, Trideceth-                                                          12                                                  __________________________________________________________________________

It is generally preferred to use emulsions having lower particle sizesas described above.

Where the silicone functional polymer is an anionic acrylate polymer orthe composition contains an anionic acrylate hair styling polymer,DC-2-1845 and DC 2-5791 are preferred emulsions. Where either of theforegoing polymers is a cationic polymer comprising nitrogen, theDC-2-8194, DC-2-1281 and/or DC 2-5932 emulsions are preferred.

Carrier

The compositions of the invention also comprise a carrier for thesilicone functional polymer and the organopolysiloxane emulsion.Suitable carriers are those in which the silicone functional polymer issoluble or dispersible, preferably soluble or microdispersible, and inwhich the organopolysiloxane is dispersible. Choice of an appropriatecarrier will also depend on the particular end use and product formcontemplated (e.g., the hair styling polymer to be used, and the productform, e.g., for hair styling compositions such as hair spray, mousse,tonic, lotion or gel). Preferred carriers are those which are suitablefor application to the hair, skin, or nails.

The carrier is present at from about 0.5% to about 99.5%, preferablyfrom about 5% to about 99.5%, most preferably from about 50% to about95%, of the composition.

The compositions of the present invention comprise one or more suitablesolvents for the silicone functional polymer. Preferred solvent systemsare those which form a homogeneous solution or dispersion (preferablymicrodispersion) with the silicone functional polymer in the weightratios used in the composition. Preferred solvent systems are thosewhich form a substantially clear to translucent solution or dispersion(preferably microdispersion) with the silicone functional polymer in theweight ratios used in the composition.

Preferred solvents include those selected from the group consisting ofwater; water soluble organic solvents; organic solvents which arestrongly to moderately strong in hydrogen-bonding parameter; andmixtures thereof; wherein the solvent is other than C₁ -C₃ monohydricalcohol, C₁ -C₃ ketone and C₁ -C₃ ether. Water is a preferred solvent.At least about 0.5%, preferably at least about 1%, of this type ofsolvent is used in the composition.

Exemplary water soluble organic solvents other than C₁ -C₃ monohydricalcohols, ketones and ethers include propylene glycol, glycerine,phenoxyethanol, dipropylene glycol, sugars, and mixtures thereof.

Solvents which are moderately strong to strong in hydrogen-bondingparameter other than C₁ -C₃ monohydric alcohols, ketones and ethersinclude esters, ethers, ketones, glycol monoethers (moderately H-bonded)and alcohols, amines, acids, amides and aldehydes (strongly H-bonded). Adescription and examples of solvents of this type are disclosed inPolymer Handbook, 2d. Ed., J. Brandrup and E. H. Immergut, Editors, JohnWiley & Sons, N.Y., 1975, Section IV, page 337-348 (Table 2). Preferredsolvents of this type are dibutyl phthalate, propylene carbonate,propylene glycol monomethyl ether, methyl acetate, methyl proprionateand mixtures thereof. Propylene glycol monomethyl ether, methyl acetate,methyl proprionate and mixtures thereof are preferred; methyl acetate ismost preferred.

Other solvents suitable for use herein are water soluble, organicvolatile solvents selected from C₁ -C₃ monohydric alcohols, C₁ -C₃ketones, C₁ -C₃ ethers, and mixtures thereof, monohydric alcohols beingpreferred. Preferred solvents of this type are methylal, ethanol,n-propanol, isopropanol, acetone and mixtures thereof. More preferredare ethanol, n-propanol, isopropanol, and mixtures thereof.

In a preferred embodiment, the carrier comprises (i) a solvent selectedfrom the group consisting of water; water soluble organic solvents;organic solvents which are strongly to moderately strong inhydrogen-bonding parameter; and mixtures thereof, wherein the solvent isother than C₁ -C₃ monohydric alcohol, C₁ -C₃ ketone and C₁ -C₃ ether;(ii) a solvent selected from the groups consisting of C₁ -C₃ monohydricalcohols, C₁ -C₃ ketones, C₁ -C₃ ethers, and mixtures thereof, and (iii)mixtures thereof, preferably a mixture thereof. Especially preferred area mixture of water and C₁ -C₃ monohydric alcohol, e.g., water-ethanol orwater-isopropanol-ethanol. Another particularly preferred solvent systemcomprises one or more of propylene glycol monomethyl ether, methylacetate, and methyl proprionate, preferably methyl acetate, optionallywith one or more of water or a C₁ -C₃ monohydric alcohol.

The carrier may include other solvents, e.g., hydrocarbons (such asisobutane, hexane, decene, acetone), halogenated hydrocarbons (such asFreon), linalool, volatile silicon derivatives, especially siloxanes(such as phenyl pentamethyl disiloxane, methoxypropyl heptamethylcyclotetrasiloxane, chloropropyl pentamethyl disiloxane, hydroxypropylpentamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane), and mixtures thereof.

Solvents used in admixture may be miscible or immiscible with eachother. However, in the final composition such solvents should becompatible with each other and other components in the composition suchthat solids do not precipitate.

Reduced "volatile organic compound" or "VOC" compositions may bedesirable. In this regard, "VOC" refers to those organic compounds thatcontain less than 12 carbon atoms or have a vapor pressure greater thanabout 0.1 mm of mercury. For example, the composition may have, asinitially applied, a total VOC content of about 95% or less, about 80%or less, about 55% or less (e.g., in preferred hairsprays), about 16% orless (e.g., in preferred mousses), or about 6% or less (e.g., inpreferred gels). The VOC may be based on actual VOC content, or the VOCwhich is delivered upon initial dispensing from a package.

Where the composition comprises a silicone graft hair styling copolymer,the compositions hereof may contain a volatile, nonpolar, branched chainhydrocarbon, which acts as a solvent for the silicone portion of thesilicone grafted copolymer. When used, the branched chain hydrocarbonsolvent hereof is present at a level of from about 0.01% to about 15%,preferably from about 0.05% to about 10%, more preferably from about0.1% to about 8%, by weight of the composition.

The branched chain hydrocarbon solvent is characterized by a boilingpoint of at least about 105° C., preferably at least about 110° C., morepreferably at least about 125° C., most preferably at least about 150°C. The boiling point is also generally about 260° C. or less, preferablyabout 200° C. or less. The hydrocarbon chosen should also be safe fortopical application to the hair and skin.

The branched chain hydrocarbon solvents are described in detail in U.S.Pat. No. 5,565,193 and are hereby incorporated by reference. The solventincludes those selected from the group consisting of C₁₀ -C₁₄ branchedchain hydrocarbons, and mixtures thereof, preferably C₁₁ -C₁₃ branchedchain hydrocarbons, more preferably C₁₂ branched chain hydrocarbons.Saturated hydrocarbons are preferred, although it isn't necessarilyintended to exclude unsaturated hydrocarbons.

Examples of suitable nonpolar solvents include isoparaffins of the abovechain sizes. Isoparaffins are commercially available from Exxon ChemicalCo. Examples include Isopar™ G (C₁₀ -C₁₁ isoparaffins), Isopar™ H and K(C₁₁ -C₁₂ isoparaffins), and Isopar™ L (C₁₁ -C₁₃ isoparaffins). The mostpreferred nonpolar solvent are C₁₂ branched chain hydrocarbons,especially isododecane. Isododecane is commercially available fromPreperse, Inc. (South Plainfield, N.J., USA) as Permethyl™ 99A.

The solubility of the silicone portion of the hair styling polymer canbe easily determined by verifying whether a silicone polymer of the samecomposition and molecular weight as that in the hair styling polymer issoluble in the nonpolar hydrocarbon solvent. In general, the siliconepolymer should be soluble at 25° C. at a concentration of 0.1% by weightof the hydrocarbon solvent, preferably at 1%, more preferably at 5%,most preferably at 15%.

The nonpolar hydrocarbon solvent, however, is insoluble in the polarsolvents of the composition. This is determined in the absence of thehair styling polymer, or other emulsifying agents, and can easily beverified by observing whether the polar and nonpolar solvents formseparate phases after being mixed together.

Without intending to be necessarily limited by any particular theory, itis believed that the nonpolar hydrocarbon solvent solubilizes thesilicone portion of the hair styling polymer. This is believed to aid inobtaining a smoother polymer film upon drying.

The carrier may also comprise conventional components such as are knownin the art suitable for a given product form.

Optional Components

Compositions of the invention may contain a variety of other ingredientssuch as are conventionally used in a given product form. Compositions ofthe present invention are especially usefhll in preparing personal careproducts, household care products, automotive care products, and coatingproducts. In the personal care area, compositions hereof include thosein the form of hair care, skin care (including underarm), and nail carecompositions. Specific examples include hair styling compositions suchas hairsprays, mousses, gels, lotions, creams, hair dressings,volumizing sprays, spray-on products such as spray-on gels, heatprotectant sprays, spritzes, pomades, and hair tonics, as well as nailpolishes, nail polish removers, wet wipe lotions, antibacterial lotion(e.g., for hand wipes), cleansing towellettes, hand sanitizers, make-upremovers, skin toners, shampoos (including 2-in-1, combined shampoos andconditioners), hair conditioners, soaps, lotions, creams, fragrances(e.g., colognes), skin cleansers, afterbath splashes, shaving creams,aftershave stick lotions, insect repellants, antiperspirants,deodorants, anti-acne products, lipsticks, foundations, mascaras, eyemake-ups, sunscreens (including spray-on sunscreens), and the like. Thecompositions may be aerosol or non-aerosol. Hair styling compositionssuch as those listed above are described, for example in California Codeof Regulations, Regulation for Reducing Volatile Organic CompoundEmissions from Consumer Products, Amendment 2, Consumer Products,Sections 94507-94717, Title 17, filed Sep. 19, 1991 and effective Oct.21, 1991; and Jellinek, J. S. Formulation and Function of Cosmetics,Wiley-Interscience (1970); each incorporated herein by reference.

For example, personal care compositions of the present invention cancontain a wide variety of other optional ingredients that are suitablefor application to human hair, skin, or nails, including among them anyof the types of ingredients known in the art for use in hair, skin, ornail care compositions, especially hair setting compositions like hairspray compositions, mousses, gels and tonics. Generally, such otheradjuvants collectively comprise from about 0.05% to about 20% by weightand preferably from about 0.1% to about 10%, by weight of thecompositions. Such conventional optional adjuvants are well known tothose skilled in the art and include, but are not limited to, hairstyling polymers, plasticizers, surfactants (which may be anionic,cationic, amphoteric or nonionic), neutralizing agents, propellants,hair conditioning agents (including polymeric and non-polymeric agents,e.g., silicone fluids, fatty esters, fatty alcohols, long chainhydrocarbons, isobutene, cationic surfactants, etc.), emollients,lubricants and penetrants such as various lanolin compounds, vitamins,proteins, preservatives, dyes, tints, bleaches, reducing agents andother colorants, sunscreens, thickening agents (e.g., polymericthickeners, such as xanthan gum), physiologically active compounds fortreating the hair, skin or nails (e.g., anti-dandruff actives, hairgrowth actives), and perfume.

Non-exclusive examples of certain types of optional components areprovided below.

a) Hair Styling Polymers

Preferred compositions are hair styling compositions containing a hairstyling polymer. As will be understood in the art, the siliconefunctional polymers described above may provide hair styling benefits.In addition to the silicone functional polymers described above, thecompositions of the present invention may comprise a or another hairstyling polymer. Suitable hair styling polymers include both siliconecontaining hair styling polymers such as described above (provided theyprovide styling properties, e.g., have a molecular weight sufficient toprovide styling properties), and non-silicone containing hair stylingpolymers. Suitable hair styling polymers are those which are soluble ormicrodispersible in the primary solvent system described herein in theweight ratios employed in the composition. Solubility is determined asdescribed in reference to the silicone functional polymer.

When used, the silicone-containing hair styling polymers are preferablypresent in a combined amount of from about 0.01% to about 20%, morepreferably from about 0.1% to about 15%, and most preferably from about1% to about 10% by weight of composition. When the hair styling polymeris a silicone graft copolymer, precopolymers include:

acrylic acid/n-butylmethacrylate/(polydimethylsiloxane (PDMS)macromer--20,000 molecular weight) (10/70/20 w/w/w) (polymer molecularweight=80-200M)

N,N-dimethylacrylamide/isobutyl methacrylate/(PDMS macromer--20,000molecular weight) (20/60/20 w/w/w)(polymer molecular weight=50-300M)

N,N-dimethylacrylamide/(PDMS macromer--20,000 molecular wt) (80/20w/w)(polymer molecular weight=50-500M)

t-butylacrylate/acrylic acid/(PDMS macromer--12,000-14,000 molecular wt)(60/20/20 w/w/w)(polymer molecular weight=120-150M)

t-butylacrylate/acrylic acid/(PDMS macromer--12,000-14,000 molecular wt)(65/25/10 w/w/w)(polymer molecular weight=100-140M)

t-butylacrylate/acrylic acid/(PDMS macromer--10,000-15,000 molecular wt)(60/20/20 w/w/w)(polymer molecular weight=50-160M)

t-butylacrylate/methacrylic acid/(PDMS macromer--12,000-14,000 molecularwt) (60/20/20 w/w/w)(polymer molecular weight=50-160M)

t-butylacrylate/acrylic acid/(PDMS macromer--2,000-5,000 molecular wt)(60/20/20 w/w/w)(polymer molecular weight=50-150M)

quaternized dimethylaminoethyl methacrylate/isobutyl methacrylate/(PDMSmacromer--10,000-15,000 molecular wt) (60/20/20 w/w/w)(polymer molecularweight=90-120 M)

Non-silicone-containing hair styling polymers include nonionic, anionic,cationic, and amphoteric polymers, and mixtures thereof. When used, thenon-silicone-containing hair styling polymers are preferably present ina combined amount of from about 0.01% to about 20%, more preferably fromabout 0.1% to about 15%, and most preferably from about 0.5% to about10% by weight of composition.

Suitable cationic polymers include Polyquaternium-4 (Celquat H-100;L200--supplier National Starch); Polyquaternium-10 (Celquat SC-240C;SC-230 M--supplier National Starch); (UCARE polymer series--JR-125,JR-400, LR-400, LR-30M, LK, supplier Amerchol ); Polyquaternium-11(Gafquat 734; 755N--supplier ISP); Polyquaternium-16 (Luviquat FC 370;FC550; FC905; HM-552 supplier by BASF);PVP/Dimethylaminoethylmethacrylate (Copolymer 845; 937; 958--ISPsupplier); Vinyl Caprolactam/PVP/Dimethylaminoethyl Methacrylatecopolymer (Gaffix VC-713; H₂ OLD EP-I--supplier ISP); Chitosan (KytamerL; Kytamer PC--supplier Amerchol); Polyquaternium-7 (Merquat550--supplier Calgon); Polyquaternium-18 (Mirapol AZ-I supplied byRhone-Poulenc); Polyquaternium-24 (Quatrisoft Polymer LM-200--supplierAmerchol); Polyquaternium-28 (Gafquat HS-100--supplier ISP);Polyquaternium-46 (Luviquat Hold--supplier BASF); and Chitosan Glycolate(Hydagen CMF; CMFP--supplier Henkel); Hydroxyethyl CetyldimoniumPhosphate (Luviquat Mono CP--supplier BASF); and Guar HydroxylpropylTrimonium Chloride (Jaguar C series -13 S, -14S, -17, 162,-2000, Hi-CARE1000--supplier Rhone-Poulenc).

Preferred cationic polymers are Polyquaternium-4; Polyquaternium-10;Polyquaternium-11; Polyquaternium-16;PVP/Dimethylaminoethylmethacrylate; VinylCaprolactam/PVP/Dimethylaminoethyl Methacrylate copolymer; and Chitosan.

Suitable amphoteric polymers includeOctylacrylmide/Acrylates/Butylaminoethyl Methacrylate Copolymer(Amphomer 28-4910, Amphomer LV-71 28-4971, Lovocryl-47 28-4947 -National Starch supplier), and Methacryloyl ethyl betaine/methacrylatescopolymer (Diaformer series supplier Mitsubishi). Preferred areOctylacrylmide/Acrylates/Butylaminoethyl Methacrylate Copolymer.

Especially preferred polymers for relatively low alcohol systems, e.g.,less than about 55% alcohol, are those which are partially zwitterionicin that they always possess a positive charge over a broad range of pHbut contain acidic groups which are only negatively charged at basic pH.Therefore the polymer is positively charged at lower pH and neutral(have both negative and positive charge) at higher pHs. Zwitterionicpolymers useful herein include Polyquaternium-47 (Merquat 2001--supplierCalgon); Carboxyl Butyl Chitosan (Chitolam NB/101--marketed by PilotChemical Company, developed by Lamberti); and Dicarboxyethyl Chitosanavailable from Amerchol as an experimental sample.

Useful nonionic polymers include PVP or Polyvinylpyrrolidone (PVP K-15,K-30, K-60, K-90, K-120--supplier ISP) (Luviskol K series 12, 17, 30,60, 80, & 90--supplier BASF); PVP/VA (PVP/VA series S-630; 735, 635,535, 335, 235--supplier ISP)(Luviskol VA); PVP/DMAPA acrylates copolymer(Styleze CC-10--supplier ISP); PVP/VA/Vinyl Propionate copolymer(Luviskol VAP 343 E, VAP 343 I, VAP 343 PM--supplier BASF);Hydroxylethyl Cellulose (Cellosize HEC--supplier Amerchol); andHydroxylpropyl Guar Gum (Jaguar HP series -8, -60, -105, -120 --supplierRhone-Poulenc).

Preferred nonionic polymers are PVP or Polyvinylpyrrolidone; PVP/VA;PVP/DMAPA acrylates copolymer; and Hydroxylpropyl Guar Gum.

Anionic polymers suitable for use herein include VA/Crotonates/VinylNeodecanonate Copolymer (Resyn 28-2930--National Starch supplier); ButylEster of PVM/MA (Gantrez A-425; ES-425; ES-435--supplier ISP); EthylEster of PVM/MA (Gantrez ES-225; SP-215--supplier ISP);Acrylates/acrylamide copolymer (Luvimer 100P; Lumiver Low VOC, supplierBASF); Methacrylate Copolymer (Balance 0/55--National Starch supplier);Vinyl Acetate/Crotonic Acid copolymer (Luviset CA 66--supplier BASF);Isopropyl Ester of PVM/MA Copolymer (Gantrez ES-335--supplier ISP);Acrylates Copolymer; Methacrylates/acrylates copolymer/amine salt(Diahold polymers--supplier Mitsubishi); 2-Butenedioic Acid (Z)-,Monoethyl Ester, Polymer with Methoxyethene (Omnirez 2000); VA/Butylmaleate/Isobornyl Acrylate (Advantage Plus terpolymer--supplier ISP);Acrylates Copolymer (Amerhold DR-25--supplier Amerchol);Acrylates/Hydroxyesteracrylates Copolymer (Acudyne 255 supplier Rohm &Haas); vinyl Acetate/Crotonic Acid/Vinyl Propionate copolymer (LuvisetCAP--supplier BASF); PVP/Acrylates copolymer (Luviflex VBM 35--supplierBASF); Diglycol/CHDM/Isophthalates/SIP Copolymer (Eastman AQ 48, AQ55--supplier Eastman Chemicals); Acrylates/Octacrylamide Copolymer(Versatyl-42 or Amphomer HC--National Starch supplier); t-butylacrylate/acrylic acid copolymer 75/25 (Mitsubishi Chemical Corp.);Acrylates Copolymer (Aculyn 33--supplier Rohm & Haas) andAcrylates/Steareth-20 Methacrylate Copolymer (Aculyn 22--Supplier Rohm &Haas) and Carbomer (supplier B.F. Goodrich).

Preferred anionic polymers are VA/Crotonates/Vinyl NeodecanonateCopolymer; Butyl Ester of PVM/MA; Ethyl Ester of PVM/MA;Acrylates/acrylamide copolymer; Methacrylate Copolymer; and VinylAcetate/Crotonic Acid copolymer.

b) Plasticizers

The compositions hereof may contain a plasticizer, e.g., for a hairstyling polymer which may be present in the composition. Any plasticizersuitable for use in hair care products or for topical application to thehair, skin or nails can be used. A wide variety of plasticizers areknown in the art. These include glycerine, diisobutyl adipate, butylstearate, propylene glycol, diethylene glycol, other glycols, tri-C₂ -C₈alkyl citrates, including triethyl citrate and analogs of triethylcitrate.

In hair styling compositions, plasticizers are typically used at levelsof from about 0.01% to about 200%, by weight of the composition,preferably from about 0.05% to about 100%, more preferably from about0.05% to about 50%, by weight of hair styling polymer.

c) Surfactants

The personal care compositions can contain one or more surfactants,e.g., for emulsifying hydrophobic components which may be present in thecomposition. Surfactants are preferred for use in mousse products.Generally, if used such surfactants will be used at a total level offrom about 0.01% to about 10%, preferably from about 0.01% to about 5%and more preferably from about 0.01% to about 3%, by weight of thecomposition. A wide variety of surfactants can be used, includinganionic, cationic, amphoteric, and zwitterionic surfactants.

Anionic surfactants include, for example: alkyl and alkenyl sulfates;alkyl and alkenyl ethoxylated sulfates; (preferably having an averagedegree of ethoxylation of 1 to 10), succinamate surfactants, such asalkylsulfosuccinamates and dialkyl esters of sulfosuccinic acid;neutralized fatty acid esters of isethionic acid; and alkyl and alkenylsulfonates, including, for example, olefin sulfonates and beta-alkoxyalkane sulfonates. Preferred are alkyl and alkenyl sulfates and alkyland alkenyl ethoxylated sulfates such as the sodium and ammonium saltsof C₁₂ -C₁₈ sulfates and ethoxylated sulfates with a degree ofethoxylation of from 1 to about 6, preferably from 1 to about 4, e.g.,lauryl sulfate and laureth (3.0) sulfate.

Amphoteric surfactants include those which can be broadly described asderivatives of aliphatic secondary and tertiary amines in which thealiphatic radical can be straight chain or branched and wherein one ofthe aliphatic substituents contains from about 8 to about 18 carbonatoms and one contains an anionic water solubilizing group, e.g.,carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples ofcompounds falling within this definition are sodium3-dodecylaminopropionate, N-alkyltaurines such as the one prepared byreacting dodecylamine with sodium isethionate according to the teachingof U.S. Pat. No. 2,658,072, N-higher allyl aspartic acids such as thoseproduced according to the teaching of U.S. Pat. No. 2,438,091, and theproducts sold under the trade name "Miranol" and described in U.S. Pat.No. 2,528,378. Others include alkyl, preferably C₆ -C₂₂ and mostpreferably C₈ -C₁₂, amphoglycinates; alkyl, preferably C₆ -C₂₂ and mostpreferably C₈ -C₁₂, amphopropionates; and mixtures thereof.

Suitable zwitterionic surfactants for use in the present compositionscan be exemplified by those which can be broadly described asderivatives of aliphatic quaternary ammonium, phosphonium, and sulfoniumcompounds, in which the aliphatic radicals can be straight chain orbranched, and wherein one of the aliphatic substituents contains fromabout 8 to 18 carbon atoms and one contains an anionicwater-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate,or phosphonate. A general formula for these compounds is: ##STR15##wherein R2 contains an alkyl, alkenyl, or hydroxy alkyl radical of fromabout 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxidemoieties and from 0 to 1 glyceryl moiety; Y is selected from the groupconsisting of nitrogen, phosphorus, and sulfur atoms; R3 is an alkyl ormonohydroxyalkyl group containing 1 to about 3 carbon atoms; x is 1 whenY is sulfur or phosphorus, 1 or 2 when Y is nitrogen; R4 is an alkyleneor hydroxyalkylene of from 1 to about 4 carbon atoms and Z is a radicalselected from the group consisting of carboxylate, sulfonate, sulfate,phosphonate, and phosphate groups. Classes of zwitterionics includealkyl amino sulfonates, alkyl betaines, and alkyl amido betaines.

Cationic surfactants useful in compositions of the present inventioncontain amino or quaternary ammonium hydrophilic moieties which arepositively charged when dissolved in the aqueous composition of thepresent invention. Cationic surfactants among those useful herein aredisclosed in the following documents, all incorporated by referenceherein: M. C. Publishing Co., McCutcheon's, Detergents & Emulsifiers,(North American edition 1979); Schwartz, et al., Surface Active Agents,Their Chemistry and Technology, New York: Interscience Publishers, 1949;U.S. Pat. No. 3,155,591, Hilfer, issued Nov. 3, 1964; U.S. Pat. No.3,929,678, Laughlin et al., issued Dec. 30, 1975; U.S. Pat. No.3,959,461, Bailey, et al., issued May 25, 1976; and U.S. Pat. No.4,387,090, Bolich, Jr., issued Jun. 7, 1983.

Among the quaternary ammonium-containing cationic surfactant materialsuseful herein are those of the general formula: ##STR16## wherein R₁ isan aliphatic group of from 1 to 22 carbon atoms, or an aromatic, aryl oralkylaryl group having from 12 to 22 carbon atoms; R₂ is an aliphaticgroup having from 1 to 22 carbon atoms; R₃ and R₄ are each alkyl groupshaving from 1 to 3 carbon atoms, and X is an anion selected fromhalogen, acetate, phosphate, nitrate and alkylsulfate radicals. Thealiphatic groups may contain, in addition to carbon and hydrogen atoms,ether linkages, and other groups such as amido groups. Other quaternaryammonium salts useful herein are diquaternary ammonium salts.

Salts of primary, secondary and tertiary fatty amines are also suitablecationic surfactants for use herein. The alkyl groups of such aminespreferably have from 12 to 22 carbon atoms, and may be substituted orunsubstituted. Secondary and tertiary amines are preferred, tertiaryamines are particularly preferred. Such amines, useful herein, includestearamido propyl dimethyl amine, diethyl amino ethyl stearamide,dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine,tridecyl amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated(5 moles E.O.) stearylamine, dihydroxy ethyl stearylamine, andarachidyl-behenylamine. Cationic amine surfactants included among thoseuseful in the present invention are disclosed in U.S. Pat. No.4,275,055, Nachtigal, et al., issued Jun. 23, 1981 (incorporated byreference herein).

Suitable cationic surfactant salts include the halogen, acetate,phosphate, nitrate, citrate, lactate and alkyl sulfate salts.

Nonionic surfactants can also be included in the compositions hereof.Nonionic surfactants include polyethylene oxide condensates of alkylphenols (preferably C₆ -C₁₂ alkyl, with a degree of ethoxylation ofabout 1 to about 6), condensation products of ethylene oxide with thereaction product of propylene oxide and ethylene diamine, condensationproducts of aliphatic alcohols with ethylene oxide, long chain (i.e.,typically C₁₂ -C₂₂) tertiary amine oxides, long chain tertiary phosphineoxides, dialkyl sulfoxides containing one long chain alkyl or hydroxyalkyl radical and one short chain (preferably C₁ -C₃) radical, siliconecopolyols, and C₁ -C₄ alkanol amides of acids having a C₈ -C₂₂ acylmoiety. Preferred nonionic surfactants are C₁ -C₄ alkanol amides ofacids having a C₈ -C₂₂ acyl moiety (e.g., Lauramide DEA), andpolyoxyethylene glycol stearyl ethers, and mixtures thereof. Specificexamples which are preferred are Lauramide DEA, Steareth-21, Steareth-2,and Sodium Cocoyl Isethionate.

Additional surfactants suitable for use herein include those describedin reference to the emulsion.

d) Neutralizing Agents

Neutralizing agents may also be used in the compositions herein. Forexample, when the personal care composition comprises a hair stylingpolymer which has acidic functionalities, such as carboxyl groups, arepreferably used in at least partially neutralized form to promotesolubility/dispersibility of the polymer. In addition, use of theneutralized form aids in the ability of the dried hair stylingcompositions to be removed from the hair by shampooing. The degree ofneutralization must balance shampoo removability versus humidityresistance. Neutralization levels in excess of what is required forshampoo removability will result in excessively sticky products thatwill not hold as well in high humidity. When available acidic monomersare neutralized, it is preferred that from about 5% to 60%, morepreferably from about 10% to about 40%, and even more preferably fromabout 12% to about 30% of the polymer (on a total polymer weight basis)be neutralized. The optimal level of neutralization for a specificpolymer will depend on the polarity of the monomers selected, thespecific ratios of the monomers to each other, and the percentage ofacidic monomers. The level of base needed to neutralize the acid groupsin a polymer for a specific % neutralization of the polymer may becalculated from the following equation:

    % Base in=A ×(B/100)×(C/D) composition

A=% Polymer in composition

B=% of polymer to be neutralized (assuming acid groups are available)

C=MW ofBase

D=MW of Acid monomer

Any conventionally used base, including organic or inorganic (metallicor other) bases, can be used for neutralization of the polymers.Metallic bases are particularly usefull in the present compositions.Hydroxides, where the cation is ammonium, an alkali metal or an alkalineearth metal, are suitable neutralizers for use in the presentcompositions. Preferred inorganic neutralizing agents for use in thecompositions of the present invention are potassium hydroxide and sodiumhydroxide. For silicone grafted hair styling polymers in compositionswith water levels >30%, sodium hydroxide is the most preferred inorganicbase. Examples of other suitable neutralizing agents which may beincluded in the personal care compositions of the present inventioninclude amines, especially amino alcohols such as2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-ethyl-1,3-propanediol(AEPD), 2-mino-2-methyl-1-propanol (AMP), 2-amino-1-butanol (AB),monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA),monoisopropanolamine (MIPA), diisopropanolamine (DIPA),triisopropanolamine (TIPA), dimethyl laurylamine (DML), dimethylmyristalamine (DMM) and dimethyl stearamine (DMS) For silicone graftedpolymers, particularly useful neutralizing agents are dimethylmyristalamine, dimethyl laurylamine, and mixtures thereof.

Hair styling or other polymers having basic functionalities, e.g., aminogroups, are preferably at least partially neutralized with an acid,e.g., hydrochloric acid.

Neutralization can be accomplished by techniques well known in the art,and before or after polymerization of the monomers comprising the hairstyling or other polymer.

e) Hair Conditioning Polymers

The compositions of the invention may include a hair conditioningpolymer for purposes of improved wet combing, dry combing and/orimproved manageability (e.g., frizz or static control). Hairconditioning polymers are typically used at a level of from about 0.001to about 6%, preferably about 0.01 to about 5%, of the composition.

Cationic and zwitterionic hair conditioning polymers are preferred.Suitable hair conditioning polymers include cationic polymers having aweight average molecular weight of from about 5,000 to about 10 million,and will generally have cationic nitrogen-containing moieties such asquaternary ammonium or cationic amino moieties, and mixtures thereof.Cationic charge density should be at least about 0.1 meq/gram,preferably less than about 3.0 meq/gram, which can be determinedaccording to the well known Kjeldahl Method. Those skilled in the artwill recognize that the charge density of amino-containing polymers canvary depending upon pH and the isoelectric point of the amino groups.The charge density should be within the above limits at the pH ofintended use. Any anionic counterions can be utilized for the cationicpolymers so long as they are compatible.

The cationic nitrogen-containing moiety will be present generally as asubstituent, on a fraction of the total monomer units of the cationichair conditioning polymers. Thus, the cationic polymer can comprisecopolymers, terpolymers, etc. of quaternary ammonium or cationicamine-substituted monomer units and other non-cationic units referred toherein as spacer monomer units. Such polymers are known in the art, anda variety can be found in International Cosmetic Ingredient Dictionary,Sixth Edition, 1995, which is incorporated by reference herein in itsentirety.

Suitable cationic polymers include, for example, copolymers of vinylmonomers having cationic amine or quaternary ammonium functionalitieswith water soluble spacer monomers such as acrylamide, methacrylamide,alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkylacrylate, alkyl methacrylate, vinyl caprolactone, and vinyl pyrrolidone.The alkyl and dialkyl substituted monomers preferably have C₁ -C₇ alkylgroups, more preferably C₁ -C₃ alkyl groups. Other suitable spacermonomers include vinyl esters, vinyl alcohol (made by hydrolysis ofpoly-vinyl acetate), maleic anhydride, propylene glycol, and ethyleneglycol. The cationic polymers are described in detail in U.S. Pat. No.4,733,677 which is hereby incorporated by reference to further describethe cationic polymers used for conditioning purposes.

The cationic amines can be primary, secondary, or tertiary amines,depending upon the particular species and the pH of the composition. Ingeneral, secondary and tertiary amines, especially tertiary amines, arepreferred. The cationic polymers can comprise mixtures of monomer unitsderived from amine- and/or quaternary ammonium-substituted monomerand/or compatible spacer monomers.

Other cationic polymers that can be used include polysaccharidepolymers, such as cationic cellulose derivatives, cationic starchderivative, and cationic guar gum derivatives. Other materials includequaternary nitrogen-containing cellulose ethers as described in U.S.Pat. No. 3,962,418, and copolymers of etherified cellulose and starch asdescribed in U.S. Pat. No. 3,958,581, which descriptions areincorporated herein by reference.

Where the composition comprises a neutralized, anionic hair stylingpolymer and a zwitterionic hair conditioning polymer, the pH of thezwitterion is preferably adjusted to that of the neutralized hairstyling polymer prior to combination therewith. Such neutralization canbe achieved by conventional methods using any conventional pH adjustingagent.

f) Propellants

Propellants may also be used in the compositions herein. For example,hair styling or other compositions according to the present inventionwhich are to be dispensed from a pressurized aerosol container (e.g.,certain hair sprays and mousses), generally comprise a propellant whichconsists of one or more of the conventionally-known aerosol propellantsto propel the compositions. A suitable propellant for use can be any gasconventionally used for aerosol containers, preferably a liquifiablegas. Suitable propellants for use are volatile hydrocarbon propellantswhich can include liquified lower hydrocarbons of 3 to 4 carbon atomssuch as propane, butane and isobutane. Other suitable propellants arehydrofluorocarbons such as 1,2-difluoroethane (Hydrofluorocarbon 152A)supplied as Dymel 152A by DuPont. Other examples of propellants aredimethylether, nitrogen, carbon dioxide, nitrous oxide, and atmosphericgas. For hair sprays and mousses, the selection of appropriatehydrocarbons is made to provide a stable system giving the desiredspray/foam quality.

The aerosol propellant may be mixed with the present compositions andthe amount of propellant to be mixed is governed by normal factors wellknown in the aerosol art. Generally, for liquifiable propellants, thelevel of propellant is from about 1% to about 60% by weight of the totalcomposition. For hair sprays, the propellant level is from about 10% toabout 60% by weight of the total composition, preferably from about 15%to about 50% by weight of the total composition. For mousses, the levelof propellant is generally from about 3% to about 30% and morepreferably from about 5% to about 15% by weight of the totalcomposition.

Alternatively, pressurized aerosol dispensers can be used where thepropellant is separated from contact with the hair styling compositionsuch as a two compartment can of the type sold under the tradename SEPROfrom American National Can Corp.

Other suitable aerosol dispensers are those characterized by thepropellant being compressed air which can be filled into the dispenserby means of a pump or equivalent device prior to use. Such dispensersare described in U.S. Pat. Nos. 4,077,441, Mar. 7, 1978, Olofsson and4,850,577, Jul. 25, 1989, TerStege, both incorporated by referenceherein, and in U.S. Ser. No. 07/839,648, Gosselin et al., filed Feb. 21,1992, also incorporated by reference herein. Compressed air aerosolcontainers suitable for use herein include those previously marketed byThe Procter & Gamble Company under their tradename VIDAL SASSOONAIRSPRAY® hair sprays.

Furthermore, non-aerosol foams may also be mixed with the presentcompositions such that the final composition is dispensable as a stablefoam. A composition is "dispensable as a stable foam" when it produces afoam when dispensed from a package or container which is eitherpressurized or equipped with an air or gas mixing device like the F2non-aerosol foamer described in U.S. Pat. Nos. 5,271,530; 5,337,929; and5,443,569; all of which are herein incorporated by reference.

g) Silicone Polyether Surfactant

Compositions of the present invention may contain a silicone polyethersuitable for stabilizing the organopolysiloxane emulsion. The siliconepolyether comprises a polymeric portion comprising repeatingorganosiloxane units, and a polymeric portion comprising repeatingalkylene oxide units (i.e., a silicone-polyoxyalkylene copolymer).Suitable silicone polyethers are those which are surface active in thecarrier employed in the compositions of the invention. As will beunderstood in the art, the surface activity of the silicone polyetherwill depend on the molecular weight of the polymeric portion comprisingrepeating organosiloxane units. This portion should be of sufficientlylarge molecular weight such that it is insoluble in the carrier, yet notso large that it renders the whole molecule insoluble in the carrier.When used, the silicone polyether is preferably used in an amount offrom about 0.02% to about 7%, more preferably about 0.05% to about 5%,of the total composition.

The silicone polyether may be a silicone--linear polyoxyalkylene blockcopolymer (wherein the polymeric backbone comprises silicone blocks andpolyoxyalkylene blocks, optionally having grafts), a silicone--graftpolyoxyalkylene copolymer (wherein the polymeric backbone comprisessilicone blocks and the polyoxyalkylene blocks are present as graftsrather than in the backbone), or a mixture thereof. Linearpolyoxyalkylene block copolymers are preferred.

Preferred silicone linear block polyethers suitable for use herein havethe formula (I):

    M'D.sub.b D'.sub.c M'

wherein

M' is a monofunctional unit R₂ R'SiO_(1/2) ;

D is a difunctional unit R₂ SiO_(2/2) ;

D' is a difunctional unit RR'SiO_(2/2) ;

R is independently H, C₁ -C₆ alkyl, or aryl, preferably H or C₁ -C₄alkyl, more preferably CH₃ ;

R' is independently, an oxyalkylene containing moiety, H, or CH₃ ;

b is an integer of from about 10 to about 1000, preferably about 10 toabout 500, more preferably about 20 to about 200; and

c is an integer of from 0 to about 100, preferably 0 to about 50, morepreferably c is 0, provided that when c is 0, at least one M' containsan oxyalkylene moiety.

Preferred R' in structure (I) are those having the formula:

    --R"(OC.sub.n CH.sub.2n).sub.y --R'"

wherein

R" is a divalent radical for connecting the oxyalkylene portion ofmoiety R' to the siloxane backbone, preferably --(C_(m) H_(2m))--,wherein m is an integer of from 2 to 8, preferably from 2-6, morepreferably from 3-6;

R'" is a terminating radical for the oxyalkylene portion of the moietyR', e.g., H, hydroxyl, C₁ -C₆ alkyl, aryl, alkoxy (e.g., C₁ -C₆) oracyloxy (e.g., C₁ -C₆), preferably hydroxyl;

n is an integer of from 2 to 4, preferably 2 to 3 (i.e., the oxyalkylenegroup may contain ethylene oxide, propylene oxide and/or butylene oxideunits); and

y is 1 or greater, wherein the total y from all the oxyalkylene moietiesin the copolymer surfactant is 10 or greater.

The oxyalkylene moiety of R' may be a random copolymer, block copolymeror a mixture thereof. Preferred R' groups in structure (I) are thosewherein the oxyalkylene units are selected from ethylene oxide units(EO), propylene oxide units (PO), and mixures thereof. More preferredare those wherein the oxyalkylene units have an ethylene oxide unit (EO)to propylene oxide unit (PO) ratio of EO₁₀₋₁₀₀ PO₀₋₁₀₀, more preferablyEO₂₀₋₇₀ PO₂₀₋₇₀, most preferably EO₃₀₋₇₀ PO₃₀₋₇₀, based on the totaloxyalkylene in the silicone polyether.

Particularly preferred silicone polyethers are those having the formula:##STR17## wherein n is an integer of from 2 to 4, x is an integer of 1or greater; a and b independently are an integer of from about 15 toabout 30; and w is an integer of from about 20 to about 200. Suchsilicone polyethers are commercially available from Goldschmidt ChemicalCompany under the tradename TEGOPREN 5830.

Preferred silicone graft polyethers for use herein are those having theformula (II):

    MD.sub.b D'.sub.c M

wherein:

M is a monofunctional unit R₃ SiO_(1/2),

D is a difunctional unit R₂ SiO_(2/2),

D' is a difunctional unit RR'SiO_(2/2),

R is independently H, C₁ -C₆ alkyl, or aryl, preferably H or C₁ -C₄alkyl, more preferably CH₃,

R' is an oxyalkylene containing moiety,

b is an integer of from about 10 to about 1000, preferably about 100 toabout 500

c is an integer of from 1 to about 100, preferably 1 to about 50.

Preferred R' are those having the formula

    --R"(OC.sub.n CH.sub.2n).sub.y --R'"

wherein

R" is a divalent radical for connecting the oxyalkylene portion ofmoiety R' to the siloxane backbone, preferably --(C_(m) H_(2m))--,wherein m is an integer of from 2 to 8, preferably 2-6, more preferably3-6;

R'" is a terminating radical for the oxyalkylene portion of moiety R',e.g., H, hydroxyl, C₁ -C₆ alkyl, aryl, alkoxy (e.g., C₁ -C₆) or acyloxy(e.g., C₁ -C₆), preferably hydroxy or acyloxy, more preferably hydroxyl;

n is an integer of from 2 to 4, preferably 2 to 3 (i.e., the oxyalkylenegroup may contain ethylene oxide, propylene oxide and/or butylene oxideunits); and

y is 1 or greater.

The oxyalkylene moiety of R' may be a random copolymer, block copolymer,or a mixture thereof. Preferred R' groups are those wherein theoxyalkylene units are selected from ethylene oxide units (EO), propyleneoxide units (PO), and mixtures thereof. More preferred are those whereinthe oxyalkylene units have an ethylene oxide unit (EO) to propyleneoxide unit (PO) ratio of EO₁₀₋₁₀₀ PO₀₋₁₀₀, more preferably EO₁₀₋₃₀PO₁₋₃₀, based on the total oxyalkylene in the silicone polyether.

In this regard, Table 1 shows some representative silicone graftpolyethers:

                  TABLE 1                                                         ______________________________________                                        Silicone                                                                      Polyether*                                                                           Structure Weight % EO                                                                              Weight % PO                                                                             HLB**                                   ______________________________________                                        A      EO        19         0         6.8                                     B      EO        40         0         8.0                                     C      EO/PO     34         0.4       6.8                                     D      EO/PO     41         12        8.2                                     E      EO/PO     34         39        5.0                                     F      EO/PO     32         42        6.4                                     G      EO/PO     30         40        5.7                                     ______________________________________                                         *Silicone Polyethers A and B contain less than 20 D units and less than       5 D' units. Silicone Polyethers CG contain from 100-200 D units and           10-30 D' units.                                                               **Hydrophilic lipophilic balance (HLB) is determined by calculating the       weight percent of EO and dividing this value by five.                    

Silicone polyethers of this type are further described in the abovereferenced patent application Ser. No. 08/929,721.

Siloxane-oxyalkylene copolymers, i.e., silicone polyethers, can beprepared according to methods generally described in the standard texton silicone chemistry entitled "Chemistry and Technology of Silicones,"by Walter Noll, Academic Press Inc., Orlando, Fla., (1968), on pages373-376. Silicone polyethers are also available from a number ofcommercial sources such as:

    ______________________________________                                                           Silicone EO       Molecular                                Trade Name                                                                             Supplier  Content %                                                                              and/or PO                                                                              Weight                                   ______________________________________                                        D.C.Q2-5220                                                                            Dow       14       EO & PO  3102                                              Corning.sup.1                                                        D.C.193  Dow       33       EO       --                                                Corning.sup.1                                                        D.C.190  Dow       24       EO & PO  2570                                              Corning.sup.1                                                        D.C. Q4-3667                                                                           Dow       37       EO       2400                                              Corning.sup.1                                                        Silwet L-7200                                                                          OSI.sup.2 31       EO & PO  19,000                                   Tegopren 5830/                                                                         Goldschmidt                                                                             55       40% EO/60%                                                                             7800                                     Abil B8830                                                                             A.G..sup.3         PO                                                Tego 5830 - A                                                                          Goldschmidt                                                                             50       30% EO/70%                                                                             9000                                              A.G..sup.3         PO                                                Tego 5830 - B                                                                          Goldschmidt                                                                             50       60% EO/40%                                                                             9000                                              A.G..sup.3         PO                                                Abil B8851                                                                             Goldschmidt                                                                             --       EO & PO  >1400                                             A.G..sup.3                                                           Abil B8863                                                                             Goldschmidt                                                                             --       EO & PO  >3000                                             A.G..sup.3                                                           Abil EM 97                                                                             Goldschmidt                                                                             75       60% EO/40%                                                                             14,000-                                  neat     A.G..sup.3         PO       15,000                                   ______________________________________                                         .sup.1 Dow Corning of Midland, Michigan                                       .sup.2 OSI Specialties of Lisle, Il.,                                         .sup.3 Hopewell, VA                                                      

From the above table, Tegopren 5830-B is preferred in compositionscontaining relatively high alcohol levels (e.g., >≈40%).

Other silicone polyethers are available as SF-1188 offered by GeneralElectric of Waterford, N.Y., and KF353A offered by Shin Etsu Siliconesof America of Torrance, Calif. Additional silicone polyethers aredescribed in U.S. Pat. No. 4,871,529, incorporated herein by reference.

Method of Making

The compositions of the present invention, including personal carecompositions, can be made using conventional formulation and mixingtechniques. In a preferred method, the silicone functional polymer andpreferably any other polymers (e.g., hair styling polymers or hairconditioning polymers), and the solvent are mixed to provide ahomogeneous mixture. Any other ingredients are then added and mixed toyield the final composition. If the polymers are neutralized, theneutralizer is preferably added prior to addition of other ingredients.For hair spray products, the composition is packaged in conventionalmechanical pump spray devices, or alternatively, in the case of aerosolsprays products, the composition is packaged in conventional aerosolcanisters along with an appropriate propellant system (also applicablefor mousses). Other hair styling compositions including tonics, lotions,and gels, are typically packaged in a conventional bottle or tube.

High water products, containing less than about 50% VOC, such as mousse(16% VOC or less) and gel (6% VOC or less), and containing a siliconehair styling copolymer derived from monomers containing acid functionalgroups are preferably prepared in the following manner. The hair stylingpolymer is dissolved in a compatible, organic solvent, e.g., ethanol orisopropanol, prior to neutralization of the polymer. The solvent used todissolve the polymer should not contain significant amounts of water andis preferably essentially free of water. If water is added prematurely,either before neutralization or before less than 10% neutralization ofthe polymer (e.g., neutralization of less than 50% of the acid groupswhere acid groups are 20% of the polymer structure), the polymer tendsto precipitate as a white insoluble mass. Attempts to completeneutralization after precipitation are generally unsuccessful.

Where water is added after neutralization has occurred, the film qualityproduced from silicone hair styling polymers modified in this mannertends to have a desirable slick and lubricious surface (withoutintending to be bound by theory, this is usually indicative of siliconepresent at the surface). Preferred compositions are substantially clearto translucent in appearance. The composition is also stable, preferablyretaining within about 10% of its initial clarity with no noticeableprecipitate formation for a period of about 6 months or more.

Completion of the neutralization reaction is important for good productclarity, good shampoo removability, and/or good stability of thecomposition. However, in compositions having low solvent levels and aneffective level of the hair styling polymer (1-5%), e.g., in typicalmousse and gel formulas, the viscosity of the system can increasedramatically with neutralization. This viscosity increase can hindercompletion of the neutralization reaction. Therefore, steps should betaken to ensure that the neutralization reaction is complete. Forexample, this can be ensured by one or more of the following techniques:

1. When the viscosity of the system becomes very thick (typically whenabout 10% of the polymer has been neutralized), a portion of the water(preferably a minimum 27% of the batch in 6% VOC systems and minimum 10%of the batch in 16% VOC systems) can be added to the system. The wateris used in an amount sufficient to lower the viscosity enough in orderto achieve good mixing.

It is preferred from the standpoint of manufacturing efficiency to addthe water portion in one step. However, the water may be added in smallincrements (e.g., 5% of the batch water), between incremental additionsof neutralizer. For example, after the first neutralizer addition(sufficient to neutralize up to about 10% of the hair styling polymer)is added with vigorous agitation, then 5% of the batch water can beadded, then enough neutralizer to neutralize another 2-4% of the hairstyling polymer can be added, then another 5% of the batch wateraddition can be made. This process continues until all the neutralizeris added to the batch. Application of high shear rates to the system,such as can be generated by a Teckmar type milling device, may also beutilized to increase the mass transfer rate, thereby resulting in fasterreaction completeness.

2. When a high viscosity has been reached a specially designed highviscosity mixing device, e.g., a dough mixer, may be used. The system ismixed for many hours until reaction completeness can verifiedanalytically (titration, FTIR, or pH), typically up to about 12 hours. Anitrogen blanketed, enclosed system or the like is preferably used tominimize solvent loss during the mix time.

3. Use specialized pressure vessel equipment, heat and agitation. Heatis to be applied while avoiding evaporation of the solvent. Therefore, anitrogen blanketed pressure vessel should be employed.

The first and third methods above are preferred as being the mostefficient. In the absence of the availability of heated pressure vessels(i.e. ambient conditions), the first method is preferred.

In addition, where the composition contains hydrophobic, oily componentssuch as perfume or isoparaffins, steps must be taken to ensure goodemulsification of the hydrophobic component in the composition. However,emulsion compositions containing alcohols can be difficult to formulate.Some hydrophobic components such as those mentioned above are relativelydifficult to emulsify, typically requiring very high levels ofsurfactants in order to create reasonably clear systems (which aretypically microemulsions). These high levels of surfactants can overplasticize the hair styling polymer, making it unacceptably sticky.

It has been found in the present invention that the hydrophobiccomponents can be readily emulsified by the use of a combination oforganic and inorganic neutralizers. Without intending to be limited bytheory, it is believed that this combination of neutralizers help thepolymer itself to function as an emulsifier by imparting surfactant-likequalities to the polymer (i.e., a portion of the polymer is relativelyhydrophobic and a portion of the polymer is relatively hydrophilic).

The neutralization system comprises a fatty amine neutralizer(preferably selected from dimethyl lauryl amine, dimethyl myristylamine, amine methyl propanol, dimethylstearyl amine, TEA, and mixturesthereof, more preferably dimethyl lauryl amine, dimethyl myristyl amineand mixtures thereof), in combination with an inorganic neutralizer(preferably metal hydroxides, more preferably NaOH and/or KOH, mostpreferably NaOH). The amine neutralized acid groups tend to be morehydrophobic than the inorganic neutralized acid groups. Withoutintending to be bound by theory, it is believed that the amine groupsemulsify the hydrophobic components and the inorganic groups providewater solubility/compatibility and shampoo removability.

When such dual neutralizers are employed, the order of componentaddition and other process variables become important for preparing theclearest, most stable product. The preferred order of addition andprocess is as follows: With vigorous agitation:

1. Completely dissolve the hair styling polymer in a compatible solventsystem containing the water soluble, organic solvent (e.g., ethanol orisopropanol).

2. Add the fatty amine neutralizer in a weight ratio of from 1-6 amineto hydrophobic components to 1-2 amine to hydrophobic components.

3. Add the hydrophobic components.

4. Add any plasticizers.

5. Add the inorganic neutralizer at a level that represents 10%-20% ofthe hair styling polymer (or 50-100% of the available acid groups in apolymer with 20% acrylic acid).

6. When the system becomes very thick (similar to peanut butter), mixthe system for at least 10 minutes. Then add water to the mixture in themanner described above, preferably as described for the preferredembodiment of the first method.

7. Mill the system with a high shear mixer such as made by Teckmar forat least 10 minutes.

8. Add the balance of the water and other ingredients required to makethe final composition. Gels are preferably dearated, more preferablybefore the addition of any thickeners.

It is important to add the silicone emulsions to the system when somewater (or other polar material) is present. The water helps to maintainthe stability of the silicone emulsions in the composition.

It is preferred to premix the silicone functional polymer with thesilicone emulsion prior to making the final compositions hereof. Wherethe silicone functional polymer is not dispersible in the emulsion, itis preferably mixed in about an equal portion of water containing from10-50% C₁ -C₃ monohydric alcohol, preferably ethanol, prior tocombination with the silicone emulsion. This pre-mix is then added tothe other ingredients of the composition which have preferably beenpre-mixed. For high monohydric alcohol systems (> about 80%), it is alsodesirable to premix the silicone emulsion with the silicone finctionalpolymer prior to combination with the alcohol.

Additionally, it is desirable to not impart high shear rates to thecomposition once the silicone emulsion has been added, since shear mightbreak the emulsion. Also, the silicone emulsion is typically added afterany thickeners or surfactants emulsion.

Method of Use

The compositions of the present invention are used in conventional waysin the intended applications, including personal care products(including hair care, skin care and nail care products), household careproducts, automotive care products and coating products.

The compositions hereof are useful, for example, in hair stylingapplications. Such applications generally involve application of aneffective amount of the product to dry, slightly damp, or wet hairbefore and/or after the hair is dried and arranged to a desired style.Application of the product is normally effected by spraying or atomizingthe product using an appropriate device, e.g. a mechanical pump spray, apressurized aerosol container, or other appropriate means. Other hairstyling compositions including tonics, lotions, and gels, are typicallydispensed from a conventional bottle or tube, and applied directly tothe hair or first dispensed to the hand and then to the hair. Thecomposition is then dried or allowed to dry. By "effective amount" ismeant an amount sufficient to provide the hair hold and style benefitsdesired. In general, from about 0.5 g to about 30 g of product isapplied to the hair, depending upon the particular product formulation,dispenser type, length of hair, and type of hair style.

Examples

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. The examples are given solelyfor the purpose of illustration and are not to be construed aslimitations of the present invention, as many variations thereof arepossible without departing from the spirit and scope of the invention.Ingredients are identified by chemical or CTFA name.

I. An insect repellent is prepared.

    ______________________________________                                        Component              Weight %                                               ______________________________________                                        Dimethyl phthalate     20                                                     n-butyl mesityl oxide oxalate                                                                        4                                                      Diethylene glycol monobutyl ether                                                                    5                                                      Polysorbate 20         10                                                     Distilled water        8.7                                                    SDA40 ethanol          40                                                     Premix                                                                        Silicone Functional Polymer - acrylic acid/n-                                                        .90                                                    butylmethacrylate/(polydimethylsiloxane                                       (PDMS) macromer-3,000 molecular weight)                                       (50/10/40 w/w/w), M.W. = 20,000                                               30% NaOH in water      .40                                                    Distilled water        8.00                                                   D.C.2-1845*            3.00                                                                          100.00                                                 ______________________________________                                         *Silicone microemulsion (25% silicone) from Dow Corning                  

The batch is prepared by preparing a premix where the water and NaOH arefirst blended. The silicone functional polymer is then added and stirredfor 1 hour. The silicone emulsion is then added and well mixed. Theremaining ingredients are put in a separate vessel and well mixed. Thepremix is then added to the main mix and stirred until homogeneous.

II. An aftershave stick lotion is prepared.

    ______________________________________                                        Component       Weight %                                                      ______________________________________                                        SDA40, ethanol  75.0                                                          Sodium stearate 6.0                                                           Glycerol        4.0                                                           Propylene glycol                                                                              3.0                                                           Perfume         0.3                                                           Menthol         0.10                                                          Distilled water 6.10                                                          Premix                                                                        Abil Si-6431*   1.00                                                          SDA 40 ethanol  1.00                                                          Distilled water 1.00                                                          DC 2-1550**     2.5                                                                           100.00                                                        ______________________________________                                         *Available from Goldschmidt                                                   **Silicone microemulsion (25% silicone) from Dow Corning                 

The Abil, water and ethanol are blended and stirred until well mixed.The microemusion is added and stirring continues until it is well mixed.The premix is then added to the main mix after all the others have beenadded and well mixed. The batch is then heated until the sodium stearatehas dissolved and then cooled down to form a stick.

III. An afterbath splash is made.

    ______________________________________                                        Component             Weight %                                                ______________________________________                                        Distilled water       25.9                                                    Perfume oil           2.50                                                    Silicone Functional Polymer - N,N-                                                                  0.50                                                    dimethylacrylamide/isobutyl                                                   methacrylate/(PDMS macromer - 2,000                                           molecular weight) (35/5/60 w/w/w),                                            M.W. = 10,000                                                                 D.C.2-1716*           1.00                                                    Laureth-23            0.30                                                    SDA 40 ethanol        69.80                                                   ______________________________________                                         *Silicone microemulsion from Dow Corning                                 

The silicone functional polymer and DC2-1716 are premixed until wellblended and added to the main mix after all the other ingredients havebeen added and mixed.

IV. A nail enamel remover is made.

    ______________________________________                                        Component              Weight %                                               ______________________________________                                        Ethyl acetate          27.00                                                  Propylene glycol       10.00                                                  Isopropyl alcohol      25.00                                                  Acetone                27.00                                                  Distilled water        8.00                                                   Premix                                                                        Silicone Functional Polymer - t-                                                                     0.50                                                   butylacrylate/acrylic acid/ DMS macromer -                                    3,000 molecular wt) (40/40/20 w/w/w),                                         M.W.= 12,000                                                                  Aminomethylpropanol    0.15                                                   Distilled water        2.00                                                   D.C.2-8676*            0.50                                                   ______________________________________                                         *Silicone microemulsion from Dow Corning                                 

The silicone functional polymer is blended with the water andaminomethylpropanol until well mixed. The microemulsion is then addedand stirred well. The premix is then added to the main mix after all theother ingredients have been well mixed.

V. A hair spray composition is made.

    ______________________________________                                                          Example V                                                   Component         %                                                           ______________________________________                                        SDA 40 Alcohol    80.00                                                       Amphomer 28-4910(1)                                                                             4.00                                                        Aminomethylpropanol(2)                                                                          0.72                                                        Silicone emulsion/                                                                              2.20                                                        Surfactant Premix 1A                                                          Distilled Water   13.08                                                       Total             100.00                                                      Silicone emulsion/                                                                              2A                                                          Surfactant Premix                                                             DC-2-1550(3)      50.00                                                       Abil Si-6431(4)   8.00                                                        SDA 40 Ethanol    21.00                                                       Distilled Water   21.00                                                       Total             100.00                                                      ______________________________________                                         (1)Commercially available from National Starch                                (2)Commercially available from Angus                                          (3)Silicone microemulsion available from Dow Corning                          (4)Available from Goldschmidt(a triblock copolymer, 3000 M.W. poly(ethyl      oxazoline)3000 M.W. poly(dimethyl siloxane) 3000 M.W. poly(ethyl              oxazoline)                                                               

Silicone Microemulsion Premix: Mix the Abil into ethanol/water untilthoroughly mixed. Add the microemulsion and stir until well blended.

Main Mixing: Add Amphomer to alcohol with vigorous agitation to aid indispersing. Once dissolved, add aminomethylpropanol followed by DROwater (if used) with moderate agitation. Add the silicone microemulsionpremix with moderate agitation and stir for additional 1/2 hour to allowthorough mixing.

VI.-VIII. A fabric softening pump spray composition (VI), a leatherconditioner composition (VII), and a pump spray lubricant for machinery(VIII) are made:

    ______________________________________                                                         Example  Example   Example                                                    V        VII       VII                                       Component        %        %         %                                         ______________________________________                                        SDA Ethanol      65.00    60.00     79.00                                     Perfume          1.25     0.10      --                                        Distilled Water  Q.S.     Q.S.      --                                        Glycerine        --       10.00     --                                                         Premix   Premix    Premix                                    N,N-dimethylacrylamide/isobutyl                                                                0.90     --        --                                        methacrylate/(PDMS macromer -                                                 2,000 molecular weight) (35/5/60                                              w/w/w), M.W. = 10,000                                                         DC-2-1845-HIPV(1)                                                                              --       --        12.00                                     DC-2-1550(2)     3.00     2.00      --                                        Abil Si-6431(3)  --       0.40      3.00                                      SDA Ethanol      --       0.40      3.00                                      Distilled Water  --       0.40      3.00                                      ______________________________________                                         (1)Silicone microemulsion from Dow Corning with a high internal phase         viscosity of 250,000 cps                                                      (2)Silicone microemulsion from Dow Corning                                    (3)A triblock copolymer from Goldschmidt of 3000 M.W. (polyethyl              oxazoline) 3000 M.W. (polydimethyl siloxane) 3000 M.W. (polyethyl             oxazoline)                                                               

Method of Making

Example VI--The silicone functional polymer and microemulsion arepremixed for one hour. The remaining ingredients are added and stirreduntil well blended, after which the premix is added with continuedstirring until well mixed.

Examples VII and VIII--The Abil is added to the water and ethanol andstirred until blended at which time the microemulsion is added withcontinued stirring. This premix is then added to the main mix, which hasthe remaining ingredients already well mixed. Stirring continues forone-half hour.

IX. Synthesis of Surface Active (Meth)Acrylate-Silicone-(Meth)AcrylateTriblock copolymers

A (meth)acrylate-sillcone-(meth)acrylate triblock copolymer is preparedaccording to the method described in "Development of Novel AttachableInitiator for Living Radical Polymerization and Synthesis ofPolysiloxane Block Copolymer;" Yoshiki Nakagawa and KrzysztofMatyjaszewski; pages 270-271; Polymer Preprints, August 1996. Somemodifications to the method are made and are described in detail below.

Vinyldimethylsilyl terminated polydimethylsiloxane is prepared accordingto the method described in the above noted reference. The vinylterminated polydimethylsiloxanes of various molecular weights areobtained from Gelest, Inc., 612 William Leigh Drive, Tullytown, Pa.19007-6308. Two different vinyldimethylsilyl terminatedpolydimethylsiloxanes are prepared using vinyl terminatedpolydimethylsiloxanes of molecular weights 9,400 and 6,000 with percentvinyl substitution of 0.8-1.2 and 0.4-0.6, respectively.

a) Block Copolymer Synthesis: Poly(n-butyl acrylate-co-methacrylicacid)-block-Polydimethylsiloxane-Poly(n-butyl acrylate-co-methacrylicacid)

Into an argon purged round-bottomed flask equiped with a magnetic strrerand reflux condenser, is added butyl acetate (500 ml),vinyldimethylsilyl terminated polydimethylsiloxane (18 g), CuCl (0.66g), 4,4'-dinonylbipyridyl (5.4 g), butyl acrylate (9 g), andtrimrthylsilylmethacrylate (9 g). The solution is then heated to 120° C.with stirring for 6 hours. The solution is then cooled to ambienttemperature and catalyst is removed via vacuum filtration. The filtrateis diluted with acetone (100 ml). The resulting solution is precipitatedinto water and the block copolymer is collected and dried.

Similar polymers are prepared in the same manner usingpolydimethylsiloxane of different molecular weights and acrylate outerblocks with various monomer combinations, e.g. variety of esters derivedfrom acrylic and methacrylic acids such as described herein. Themonomers of the acrylate outer blocks may be selected such that theouter blocks have a Tg above or below ambient temperature (about 23°C.).

What is claimed is:
 1. A personal care composition suitable forapplication to the hair, skin or nails comprising:a) a siliconefunctional polymer having the formula selected from the group consistingof: (AB)_(n) ; ABA; BAB; ##STR18## and mixtures thereof; wherein B is asilicone moiety comprising repeating units of: ##STR19## R isindependently, C1-C30 alkyl, aryl, alkylaryl, haloalkyl, H, or C1-C6alkoxy, wherein the weight average molecular weight of each siliconemoiety B is independently from about 1500 to about 50,000; A is a polarpolymeric moiety which is soluble or dispersible in mixtures of ethanoland water containing less than 60% ethanol by weight; n is an integer of1 or greater;wherein the molecular weight of the silicone functionalpolymer is at least about 2,000; b) an organopolysiloxane emulsioncomprising: (i) a polyorganosiloxane dispersed as particles in theemulsion, the polyorganosiloxane having an average particle size of lessthan about 150 nanometers, wherein the polyorganosiloxane contains thedifunctional repeating unit which corresponds to the general formula:##STR20## wherein n is greater than 1 and R¹ and R² are eachindependently C₁ -C₇ alkyl or phenyl, and wherein the degree ofpolymerization of the polysiloxane is in the range of from 10 to 3,000;and (ii) a surfactant system for dispersing the organopolysiloxane inthe emulsion; c) a carrier comprising (i) at least about 0.5%, by weightof the composition, of a first solvent selected from the groupconsisting of water; water soluble organic solvents; organic solventswhich are strongly to moderately strong in hydrogen-bonding parameter;and mixtures thereof; wherein the first solvent is other than C₁ -C₃monohydric alcohol, C₁ -C₃ ketone and C₁ -C₃ ether, and (ii) at leastabout 40%, by weight of the composition, of a second solvent selectedfrom the group consisting of C₁ -C₃ monohydric alcohols, C₁ -C₃ ketones,C₁ -C₃ ethers, and mixtures thereof;wherein the silicone functionalpolymer is present in an amount effective to stabilize the emulsion inthe personal care composition.
 2. The composition of claim 1 wherein theweight average molecular weight of each silicone moiety B isindependently from about 2,000 to about 40,000.
 3. The composition ofclaim 2 wherein the weight average molecular weight of each siliconemoiety B is independently from about 2,000 to about 30,000.
 4. Thecomposition of claim 1 wherein A is selected from the group consistingof acrylic polymers, vinyl polymers, polyalkyloxazolines, proteins,sugars, polysaccharides and mixtures thereof.
 5. The composition ofclaim 4 wherein A is selected from the group consisting of acrylicpolymers, vinyl polymers, polyalkyloxazolines, and mixtures thereof. 6.The composition of claim 1 wherein the molecular weight of the siliconefunctional polymer is from about 2,000 to about 150,000.
 7. Thecomposition of claim 6 wherein the molecular weight of the siliconefunctional polymer is from about 3,000 to about 50,000.
 8. Thecomposition of claim 7 wherein the molecular weight of the siliconefunctional polymer is from about 3,000 to about 20,000.
 9. Thecomposition of claim 1 wherein the silicone functional polymer is asilicone graft copolymer having a vinyl polymeric backbone comprisingacrylate groups having grafted to it monovalent siloxane polymericmoieties, the copolymer comprising C monomers and components selectedfrom the group consisting of A monomers, B monomers, and mixturesthereof, wherein:A is at least one free radically polymerizable vinylmonomer, the amount by weight of A monomer, when used, being up to about90% by weight of the total weight of all monomers in said copolymer; Bis at least one reinforcing monomer copolymerizable with A, the amountby weight of B monomer, when used, being up to about 98% of the totalweight of all monomers in said copolymer, said B monomer being selectedfrom the group consisting of polar monomers and macromers; at least oneof said A or B monomers comprising acrylate groups; and C is a polymericmonomer having a weight average molecular weight of from about 1,500 toabout 50,000 and the general formula

    X(Y).sub.n Si(R).sub.3-m (Z).sub.m

wherein X is a vinyl group copolymerizable with the A and B monomers, Yis a divalent lining group, R is a hydrogen, lower alkyl, aryl oralkoxy, Z is a monovalent siloxane polymeric moiety having a numberaverage molecular weight of at least about 500, is essentiallyunreactive under copolymerization conditions, and is pendant from saidvinyl polymeric backbone after polymerization, n is 0 or 1, m is aninteger from 1 to 3,wherein C comprises from about 0.01% to about 50% byweight of the copolymer.
 10. The composition of claim 9 wherein thesilicone functional polymer is selected from the group consisting of:(A)acrylic acid/n-butylmethacrylate/(polydimethylsiloxane (PDMS)macromer-3,000 molecular weight) (50/10/40 w/w/w), M.W.=20,000; (B)N,N-dimethylacrylamide/isobutyl methacrylate/(PDMS macromer-2,000molecular weight) (35/5/60 w/w/w), M.W.=10,000; (C)N,N-dimethylacrylamide/(PDMS macromer-4,000 molecular weight) (80/20w/w), M.W.=20,000; (D) t-butylacrylate/acrylic acid/(PDMS macromer-3,000molecular weight) (40/40/20 w/w/w), M.W.=12,000; (E)t-butylacrylate/acrylic acid/(PDMS macromer-12,000-14,000 molecularweight) (65/25/10 w/w/w), M.W.=80,000; and (F) mixtures thereof.
 11. Thecomposition of claim 1 wherein A is a polyalkyloxazoline.
 12. Thecomposition of claim 11 wherein the silicone functional polymer is atriblock copolymer of 3000 M.W. (polyethyl oxazoline)-3000 M.W.(polydimethyl siloxane)-3000 M.W. (polyethyl oxazoline).
 13. Thecomposition of claim 1 wherein the average particle size of thedispersed polyorganosiloxane is about 60 nanometers or less.
 14. Thecomposition of claim 13 wherein the average particle size of thedispersed polyorganosiloxane is about 40 nanometers or less.
 15. Thecomposition of claim 1 wherein the first solvent is water.
 16. Thecomposition of claim 1 wherein the second solvent is a C₁ -C₃ monohydricalcohol.
 17. The composition of claim 16 wherein the monohydric alcoholis selected from the group consisting of ethanol, n-propanol,isopropanol and mixtures thereof.
 18. The composition of claim 17wherein the first solvent is water.
 19. The composition of claim 1wherein the composition comprises from about 0.01% to about 20% of thesilicone functional polymer.
 20. The composition of claim 19 wherein theamount of emulsion is such that the personal care composition comprisesfrom about 0.01% to about 10% of the dispersed polyorganosiloxane. 21.An emulsion composition comprising:a) a silicone functional polymerhaving the formula selected from the group consisting of: (AB)_(n) ;ABA; BAB; ##STR21## and mixtures thereof; wherein B is a silicone moietycomprising repeating units of: ##STR22## R is independently, C1-C30alkyl, aryl, alkylaryl, haloalkyl, H, or C1-C6 alkoxy, wherein theweight average molecular weight of each silicone moiety B isindependently from about 1500 to about 50,000; A is a polar polymericmoiety which is soluble or dispersible in mixtures of ethanol and watercontaining less than 60% ethanol by weight; n is an integer of 1 orgreater;wherein the molecular weight of the silicone functional polymeris at least about 2,000; b) an organopolysiloxane emulsion comprising:(i) a polyorganosiloxane dispersed as particles in the emulsion, thepolyorganosiloxane having an average particle size of less than about150 nanometers, wherein the polyorganosiloxane contains the difunctionalrepeating unit which corresponds to the general formula: ##STR23##wherein n is greater than 1 and R¹ and R² are each independently C₁ -C₇alkyl or phenyl, and wherein the degree of polymerization of thepolysiloxane is in the range of from 10 to 3,000; and (ii) a surfactantsystem for dispersing the organopolysiloxane in the emulsion; c) acarrier comprising (i) at least about 0.5%, by weight of thecomposition, of a first solvent selected from the group consisting ofwater; water soluble organic solvents; organic solvents which arestrongly to moderately strong in hydrogen-bonding parameter; andmixtures thereof; wherein the first solvent is other than C₁ -C₃monohydric alcohol, C₁ -C₃ ketone and C₁ -C₃ ether, and (ii) at leastabout 40%, by weight of the composition, of a second solvent selectedfrom the group consisting of C₁ -C₃ monohydric alcohols, C₁ -C₃ ketones,C₁ -C₃ ethers, and mixtures thereof;wherein the silicone functionalpolymer is present in an amount effective to stabilize the emulsion inthe composition.
 22. A personal care product containing the emulsion ofclaim
 21. 23. A household care product containing the emulsion of claim21.
 24. An automotive care product containing the emulsion of claim 21.25. A coating product containing the emulsion of claim 21.